KR102303879B1 - Multilayer structure and production method therefor - Google Patents

Abstract

The disclosed multilayered structure is a multilayered structure each having one or more layers of the substrate (X), the layer (Y), and the layer (Z). Layer (Y) contains aluminum atoms. The layer (Z) contains a polymer (E) having a plurality of phosphorus atoms. The polymer (E) is a polymer of at least one monomer containing vinylphosphonic acids. At least one set of layers (Y) and (Z) are laminated adjacently. The layer (Z) is formed by applying a coating solution (V) which is a solution of a polymer (E) having a plurality of phosphorus atoms. The disclosed multilayer structure has excellent gas barrier properties, and can maintain gas barrier properties at a high level even when subjected to physical stress such as deformation or impact.

Description

Multilayer structure and manufacturing method thereof

The present invention relates to a multilayer structure and a method for manufacturing the same.

A laminate in which a film composed of aluminum and its oxide, alumina, as a constituent component, is formed on a plastic film is well known in the past, and as a packaging material having gas barrier properties for protecting items that are easily deteriorated by oxygen, including food. is being used Most of these gas barrier films are formed from plastic films by dry processes such as vacuum deposition, sputtering, ion plating, and chemical vapor deposition (CVD). An aluminum vapor deposition film has light-shielding property in addition to gas-barrier property, and is mainly used as a packaging material for dry foodstuffs. On the other hand, the alumina vapor deposition film having transparency has the visibility of the contents, and taking advantage of features such as foreign material inspection by a metal detector or microwave heating, it is used as a packaging material in a wide range of applications, including retort food packaging.

Moreover, the transparent gas barrier film comprised by an aluminum atom, an oxygen atom, and a sulfur atom is known (patent document 1: Unexamined-Japanese-Patent No. 2003-251732). Japanese Patent Application Laid-Open No. 2003-251732 discloses that a transparent film having gas barrier properties is formed on a plastic film by using aluminum as a target and a mixed gas of hydrogen sulfide and oxygen as a reaction gas, and by a reactive sputtering method. method is disclosed.

Further, a transparent gas barrier film constituted of a reaction product of alumina particles and a phosphorus compound is disclosed by the present inventors (Patent Document 2: International Publication No. WO2011-122036). International Publication No. WO2011-122036 discloses a method for forming a transparent film having gas barrier properties on a plastic film by applying a coating solution containing alumina particles and a phosphorus compound, followed by drying and heat treatment.

Japanese Laid-Open Patent Publication No. 2003-251732 International Publication No. WO2011-122036

However, the conventional gas barrier film has excellent initial gas barrier properties, but when subjected to physical stress such as deformation or impact, defects such as cracks and pinholes may occur, and gas barrier properties are insufficient in actual use. there was a case For example, when used as a food packaging material, it is subjected to various physical stresses in each stage of printing, laminating, woven, food filling, transportation, display, and consumption. For this reason, there is a demand for a multilayer structure capable of maintaining high gas barrier properties even when subjected to such physical stress.

Therefore, one of the objects of the present invention is to provide a multilayer structure that has excellent gas barrier properties and can maintain gas barrier properties at a high level even when subjected to physical stress such as deformation or impact, and a method for manufacturing the same.

As a result of repeated studies in order to achieve the above object, the present inventors have excellent gas barrier properties by laminating a layer having an aluminum atom and a layer containing a polymer having a plurality of phosphorus atoms adjacent to each other, resulting in deformation and impact It has been found that a multilayered structure capable of maintaining the gas barrier properties at a high level even when subjected to physical stress such as . That is, by laminating a layer containing a polymer having a plurality of phosphorus atoms having no gas barrier properties adjacent to a layer having aluminum atoms having gas barrier properties, the bending resistance of the obtained multilayered structure could be significantly improved. By repeating further examination based on this new knowledge, the present inventors completed this invention.

That is, the multilayered structure of the present invention is a multilayered structure each having one or more layers of a substrate (X), a layer (Y) and a layer (Z), wherein the layer (Y) contains an aluminum atom, The layer (Z) contains a polymer (E) having a plurality of phosphorus atoms, the polymer (E) is a polymer of at least one monomer containing vinylphosphonic acids, and at least one set of the layer (Y) and the layer (Z) are stacked adjacent to each other.

In the multilayered structure of the present invention, at least one set of the substrate (X), the layer (Y), and the layer (Z) is in the order of the substrate (X)/the layer (Y)/the layer (Z) It may have a laminated structure.

In the multilayer structure of the present invention, the polymer (E) may be polyvinylphosphonic acid represented by the following formula (I).

[Formula I]

In the above formula (I),

n is a natural number.

In the multilayer structure of the present invention, the layer (Y) may be a layer (YA) containing a reaction product (R). The reaction product (R) is a reaction product formed by reacting a metal oxide (A) containing aluminum and a phosphorus compound (B), and in the infrared absorption spectrum of the layer (YA), in the range of ^{800 to 1400 cm -1 The wavenumber (n 1} ) at which the absorption of infrared rays is maximized may be in the range of 1080 to 1130 cm ^{-1 .}

In the multilayer structure of the present invention, in the infrared absorption spectrum of the layer (YA), the ^{absorbance (α 1 ) at the wave number (n 1} ) and the absorbance (α ² ) at the wave number (n ² ) are, The relationship of absorbance (α ² )/absorbance (α ¹ ) ≤ 0.2 may be satisfied. The wave number n ² is a wave number at which infrared absorption based on stretching vibration of a hydroxyl group in the range of ^{2500 to 4000 cm −1} in the infrared absorption spectrum of the layer YA becomes maximum.

In the multilayer structure of the present invention, the half-width of the absorption peak at ^{the wavenumber n 1 may be 200 cm -1} or less.

In the multilayer structure of the present invention, the metal oxide (A) may be a hydrolysis-condensation product of a compound (L) containing a metal atom (M) to which a hydrolyzable characteristic group is bonded, and the compound (L) is You may contain at least 1 sort(s ^{) of compound (L<1>) represented by general formula (II).}

[Formula II]

In the above formula (II),

X ¹ is selected from the group consisting of F, Cl, Br, I, R ² O-, R ³ C(=O)O-, (R ⁴ C(=O)) ₂ CH- and NO _{3 .} R ¹ , R ² , R ³ and R ⁴ are each selected from the group consisting of an alkyl group, an aralkyl group, an aryl group and an alkenyl group. In the general formula (II), when a plurality of X ^1s exist, these X ^1s may be the same as or different from each other. In general formula (II), when a plurality of R ¹ is present, these R ¹ may be the same as or different from each other. In the general formula (II), when a plurality of R ^{2 s} exist, these R ² may be the same as or different from each other. In formula (II), when a plurality of R ³ is present, these R ³ may be the same as or different from each other. In the general formula (II), when a plurality of R ⁴ is present, these R ⁴ may be the same as or different from each other. m represents the integer of 1-3.

In the multilayer structure of the present invention, the compound (L ¹ ) may be at least one compound selected from aluminum triisopropoxide and aluminum tris-butoxide.

In the multilayer structure of the present invention, the phosphorus compound (B) may be at least one compound selected from the group consisting of phosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid and derivatives thereof.

In the multilayer structure of the present invention, in the layer (YA), the number of moles (N _M ) of metal atoms (M) constituting the metal oxide (A) and the number of moles of phosphorus atoms derived from the phosphorus compound (B) (N _P) is, 1.0≤ (the mole number (N _M)) / (the mole number (N _P)) is good even when meeting the relation of ≤3.6.

In the multilayer structure of the present invention, the layer (Y) may be a vapor-deposited layer of aluminum or a vapor-deposited layer of aluminum oxide.

In the multilayer structure of the present invention, the substrate (X) may contain at least one layer selected from the group consisting of a thermoplastic resin film layer, a paper layer, and an inorganic vapor deposition layer.

The multilayer structure of the present invention may have an oxygen permeability of 2 ml/(m 2 ·day·atm) or less under the conditions of 20°C and 85%RH.

The multilayered structure of the present invention has an oxygen permeability of 4 ml/(m 2 ·day · atm) or less.

The manufacturing method of the present invention is a method for manufacturing a multilayer structure each having one or more layers of a substrate (X), a layer (Y), and a layer (Z), wherein the layer (Y) contains an aluminum atom, and the layer (Z) contains a polymer (E) having a plurality of phosphorus atoms, the polymer (E) is a polymer of at least one monomer containing vinylphosphonic acids, and at least one set of the layer (Y); and a step (IV) of forming the layer (Z) by applying a coating solution (V) in which the layers (Z) are laminated adjacently and containing the polymer (E).

In the production method of the present invention, the polymer (E) may be polyvinylphosphonic acid represented by the following formula (I).

Formula I

In the above formula (I),

n is a natural number.

In the production method of the present invention, the layer (Y) may be a layer (YA) containing a reaction product (R), and the reaction product (R) is a metal oxide (A) containing aluminum and a phosphorus compound ( A reaction product formed by the reaction of B) may be used. In this case, the manufacturing method of this invention mixes the said metal oxide (A), at least 1 sort(s) of compound containing the site|part which can react with the said metal oxide (A), and a solvent, The said metal oxide (A), Step (I) of preparing a coating solution (U) containing the at least one compound and the solvent;

Step (II) of forming a precursor layer of the layer (YA) on the substrate (X) by applying the coating solution (U) on the substrate (X);

You may further include the process (III) of heat-processing the precursor layer of the said layer (YA) at a temperature of 110 degreeC or more to form the said layer (YA). The said at least 1 sort(s) of compound may contain the said phosphorus compound (B). In the above coating liquid (U), the molar number (N _M) and a mol number (N _P) of phosphorus atoms contained in the compound of (B) of the metal atom (M) constituting the metal oxide (A), 1.0 The relationship of ? (the number of moles (N _M ))/(the number of moles (N _P )) ? 3.6 may be satisfied.

In the manufacturing method of this invention, you may implement the said process (IV) after the said process (III).

In the manufacturing method of this invention, the vapor-deposited layer of aluminum or the vapor-deposited layer of aluminum oxide may be sufficient as the said layer (Y).

According to the present invention, a multilayer structure having excellent gas barrier properties and capable of maintaining gas barrier properties at a high level even when subjected to physical stress such as deformation or impact can be obtained. Moreover, according to the manufacturing method of this invention, the said multilayered structure can be manufactured easily.

In addition, in this specification, even when it receives physical stress, such as a deformation|transformation and an impact, the property which can maintain gas barrier property at a high level may be expressed as "flexibility resistance". In addition, in this specification, "gas-barrier property after hold|maintaining for 5 minutes in the state extended 5% under the conditions of 23 degreeC and 50%RH" was employ|adopted as an index|index for evaluating bending resistance. This is an evaluation condition that is harsher than the physical stress that can occur under normal practical conditions, and it can be expected that a multilayer structure showing good evaluation results with this index shows good performance also in practical use.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described. In addition, although specific materials (compounds, etc.) may be illustrated as a material which expresses a specific function in the following description, this invention is not limited to the form using such a material. In addition, unless there is a description in particular, 1 type may be used independently and 2 or more types may be used together as for the illustrated material.

[Multilayer structure]

The multilayered structure of the present invention is a multilayered structure each having one or more layers of a substrate (X), a layer (Y) and a layer (Z), wherein the layer (Y) contains an aluminum atom, and the layer (Z) contains a phosphorus atom It contains a plurality of polymers (E), wherein the polymer (E) is a polymer of at least one monomer containing vinylphosphonic acids, and at least one set of layers (Y) and (Z) are laminated adjacently. has been Such a multilayer structure is obtained by the method of the present invention for producing a multilayer structure.

[Floor (Y)]

The layer (Y) included in the multilayer structure of the present invention may be a layer (YA) containing at least a reaction product (R) formed by reacting a metal oxide (A) containing aluminum and a phosphorus compound (B). Alternatively, the layer (Y) may be a layer (hereinafter, sometimes referred to as “layer (YB)”) which is a vapor-deposited layer of aluminum or a vapor-deposited layer of aluminum oxide (hereinafter referred to as “layer (YC)”). yes) is fine. Hereinafter, it demonstrates in order.

[Floor (YA)]

When the layer (Y) of the multilayer structure of the present invention is the layer (YA), in the infrared absorption spectrum of the layer (YA), the wavenumber (n) at which the infrared absorption becomes the maximum in the range of ^{800 to 1400 cm -1 1} ) may be in the range of 1080 to 1130 cm ^{-1 .}

Hereinafter the art wave number (n ^1),, there is a case called "the maximum absorption wave number (n ^1)." A metal oxide (A) reacts with a phosphorus compound (B) in the form of particle|grains of a metal oxide (A) normally.

Typically, the layer (YA) included in the multilayer structure of the present invention has a structure in which particles of the metal oxide (A) are bonded to each other via a phosphorus atom derived from the phosphorus compound (B). The form bonding through a phosphorus atom includes a form bonding through an atomic group containing a phosphorus atom, for example, bonding through an atomic group containing a phosphorus atom and not containing a metal atom form is included.

In the layer (YA) of the multilayered structure of the present invention, the number of moles of metal atoms not derived from the metal oxide (A) as the metal atoms bonding the particles of the metal oxide (A) is the number of moles of the metal oxide (A) It is preferable to exist in the range of 0 to 1 times (for example, the range of 0 to 0.9 times) the number of moles of phosphorus atoms bonding the particles to each other, for example, 0.3 times or less, 0.05 times or less, 0.01 times or less, Or 0 times may be sufficient.

The layer (YA) included in the multilayered structure of the present invention may partially contain the metal oxide (A) and/or the phosphorus compound (B) that are not involved in the reaction.

In general, when a metal compound and a phosphorus compound react to form a bond represented by MOP in which a metal atom (M) constituting the metal compound and a phosphorus atom (P) derived from the phosphorus compound are bonded through an oxygen atom (O) , a characteristic peak occurs in the infrared absorption spectrum. Here, the characteristic peak shows an absorption peak at a specific wavenumber according to the environment or structure around the bond. As a result of studies by the present inventors, it was found that, when the absorption peak based on the binding of MOP ^{was located in the range of 1080 to 1130 cm -1} , excellent gas barrier properties were expressed in the obtained multilayer structure. In particular, when the absorption peak appears as an absorption peak with the maximum absorption wave number in the region of ^{800 to 1400 cm -1} in which absorption derived from bonding of various atoms and oxygen atoms is generally exhibited, the obtained multilayer structure is more excellent. It turned out that gas barrier property expresses.

In addition, although this invention is not limited at all, the particle|grains of a metal oxide (A) are interposed through the phosphorus atom derived from a phosphorus compound (B), and also metal atoms which do not originate in a metal oxide (A) are interposed. When a bond represented by MOP is formed, in which a metal atom (M) and a phosphorus atom (P) constituting the metal oxide (A) are bonded through an oxygen atom (O), the metal oxide (A) Due to the relatively constant environment of the particle surface, in the infrared absorption spectrum of the layer (YA), the absorption peak based on the binding of MOP is in ^{the range of 1080 to 1130 cm -1} and 800 to 1400 cm ^{-1 in} the region. It is considered that it appears as an absorption peak of the maximum absorption wave number in the present invention.

On the other hand, when hydrolysis-condensation is carried out after mixing previously the phosphorus compound (B) with the metal compound which does not form metal oxides, such as a metal alkoxide and a metal salt, the metal atom derived from a metal compound, and a phosphorus compound (B) In the infrared absorption spectrum, the maximum absorption wave number (n ^{1 ) in the range of 800 to 1400 cm -1 is out} of the range of 1080 to 1130 cm ^-1 .

The maximum absorption wave number (n ¹⁾ is, since the gas barrier property is more excellent multi-layer structure, and preferably in the range of 1085 to 1120cm ^-1, and more preferably in the range of 1090 to 1110cm ^-1.

In the infrared absorption spectrum of the layer (YA) of the multilayered structure of the present invention, absorption of stretching vibrations of hydroxyl groups bonded to various atoms may appear in the range of ^{2500 to 4000 cm -1 .} Examples of the hydroxyl group exhibiting absorption in this range include a hydroxyl group present on the surface of the metal oxide (A) portion and having the form of M-OH, a phosphorus atom (P) derived from the phosphorus compound (B) to form P-OH The hydroxyl group which has a form, the hydroxyl group which has the form of C-OH derived from the polymer (C) mentioned later, etc. are mentioned. The amount of hydroxyl groups present in the layer YA can be related to the absorbance α ^{2 at the wavenumber n 2} of the maximum absorption based on the stretching vibration of the hydroxyl group in the range of ^{2500 to 4000 cm −1 .} Here, the wave number n ² is the wave number at which the infrared absorption based on the stretching vibration of the hydroxyl group in the range of ^{2500 to 4000 cm -1} in the infrared absorption spectrum of the layer YA becomes the maximum. In the following, there is a case that the wave number (n ^2), "the maximum absorption wave number (n ^2)".

As the amount of hydroxyl groups present in the layer (YA) increases, the density of the layer (YA) decreases, and as a result, the gas barrier property tends to decrease. In addition, in the infrared absorption spectrum of the layer (YA) of the multilayer structure of the present invention, the ratio of the absorbance (α ¹ ) to the absorbance (α ^{2 ) at the maximum absorption wave number (n 1} ) [absorbance (α ^{2 )} )/absorbance (α ¹ )], it is considered that the particles of the metal oxide (A) are effectively bonded to each other via the phosphorus atom derived from the phosphorus compound (B). For this reason, the ratio [absorbance (α ² )/absorbance (α ¹ )] is preferably 0.2 or less, and more preferably 0.1 or less, from the viewpoint of highly expressing the gas barrier properties of the obtained multilayered structure. The multilayer structure in which the layer (YA) has the above ratio [absorbance (α ² )/absorbance (α ¹ )] is the number of moles of metal atoms constituting the metal oxide (A) described later (N _M ) and a phosphorus compound ( It can be obtained by adjusting the ratio of the number _{of moles (NP} ) of phosphorus atoms derived from B), heat treatment conditions, and the like. In addition, although not particularly limited, in the infrared absorption spectrum of the precursor layer of the layer (YA) to be described later, the maximum absorbance (α ^{1 ' ) in the range of 800 to 1400 cm -1 , and in} the range of 2500 to 4000 cm ^{-1 The maximum absorbance (α 2′} ) based on the stretching vibration of the hydroxyl group of , sometimes satisfies the relationship of absorbance (α ^2′ )/absorbance (α ^{1′ ) > 0.2.}

In the infrared absorption spectrum of the layer (YA) of the multilayer structure of the present invention, the ^{half width of the absorption peak having a maximum at the maximum absorption wavelength (n 1 ) is 200 cm -1} from the viewpoint of the gas barrier properties of the obtained multilayer structure or less, it is preferable, 150cm ^-1, and more preferably less than or equal, more preferably less than or equal to 130cm ^-1, more preferably less than or equal to 110cm ^-1, and more preferably less than or equal to 100cm ^-1, it is particularly preferred not more than 50cm ^-1. Although the present invention is not limited in any way, when the particles of the metal oxide (A) are bonded via a phosphorus atom, the particles of the metal oxide (A) are bonded to each other via a phosphorus atom derived from the phosphorus compound (B). , also bonded without interposing a metal atom not derived from the metal oxide (A), and the metal atom (M) and the phosphorus atom (P) constituting the metal oxide (A) are bonded through an oxygen atom (O) When a bond represented by MOP is generated, due to a relatively constant environment called the surface of the metal oxide (A) particle, it is thought that the half-width of the absorption peak having a maximum in the ^{maximum absorption wave number (n 1 ) will be in the above range} . In the present specification, the half-width of the absorption peak of the ^{maximum absorption wavenumber (n 1} ) is a two-point wavenumber having an absorbance (absorbance (α ^{1 )/2) of half of the absorbance (α 1 ) in the absorption peak.} It can be obtained by finding and calculating the difference.

The infrared absorption spectrum of the layer (YA) can be obtained by measuring by the ATR method (total reflection measurement method), or by cutting the layer (YA) from the multilayer structure and measuring the infrared absorption spectrum by the KBr method.

In the layer (YA) included in the multilayer structure of the present invention, the shape of each particle of the metal oxide (A) is not particularly limited, and examples thereof include a spherical shape, a flat shape, a polyhedral shape, a fibrous shape, and a needle shape. It is preferably in the form of a fibrous or needle-like multilayer structure because it provides a more excellent gas barrier property. The layer (YA) may have only particles having a single shape, or may have particles having two or more different shapes. In addition, the size of the particles of the metal oxide (A) is not particularly limited, either, and can be exemplified from a nanometer size to a submicron size. It is preferable that a size exists in the range of 1-100 nm as an average particle diameter.

In addition, the microstructure as described above in the layer (YA) of the multilayered structure of the present invention can be confirmed by observing the cross section of the layer (YA) with a transmission electron microscope (TEM). In addition, the particle diameter of each particle of the metal oxide (A) in the layer (YA) is the longest axis of each particle in the cross-sectional observation image of the layer (YA) obtained with a transmission electron microscope (TEM). can be obtained as an average value of the maximum length of , and the maximum length of the particles on an axis perpendicular to it .

In the layer (YA) of the multilayered structure of the present invention, in one example, the particles of the metal oxide (A) are interposed with a phosphorus atom derived from the phosphorus compound (B), and are not derived from the metal oxide (A). It has a bonded structure without intervening metal atoms. That is, in an example, although the particle|grains of a metal oxide (A) may couple|bond via the metal atom originating in a metal oxide (A), it has a structure couple|bonded without interposing other metal atoms. Here, the "structure bonded via a phosphorus atom derived from the phosphorus compound (B) and not via a metal atom not derived from the metal oxide (A)" is a bond between particles of the metal oxide (A) to be bonded. means a structure in which the main chain has a phosphorus atom derived from the phosphorus compound (B) and does not have a metal atom not derived from the metal oxide (A), including structures having a metal atom in the side chain of the bond do. However, the layer (YA) included in the multilayer structure of the present invention has a structure in which particles of the metal oxide (A) are bonded via both a phosphorus atom and a metal atom derived from the phosphorus compound (B) (metal to be bonded) The main chain of the bond between the particles of the oxide (A) may have a part of the structure having both a phosphorus atom and a metal atom derived from the phosphorus compound (B).

In the layer (YA) included in the multilayered structure of the present invention, as a bonding form of each particle of the metal oxide (A) and a phosphorus atom, for example, a metal atom (M) and a phosphorus atom constituting the metal oxide (A) A form in which (P) is bonded via an oxygen atom (O) is mentioned. The particles of the metal oxide (A) may be bonded via a phosphorus atom (P) derived from one molecule of the phosphorus compound (B), but via a phosphorus atom (P) derived from two or more molecules of the phosphorus compound (B) and may be combined. As a specific bonding form between the particles of the two metal oxides (A) that are bonded, the metal atoms constituting the particles of one metal oxide (A) that are bonded are represented by (Mα), and the other metal oxide (A) is When the metal atom constituting the particle is represented by (Mβ), for example, the bonding form of (Mα)-OPO-(Mβ); the binding form of (Mα) _{-OP-[OP] n} -O-(Mβ); the bound form of (Mα)-OPZPO-(Mβ); and the binding form of (Mα)-OPZP-[OPZP] _{n -O-(Mβ).} In addition, in the example of the said bonding form, n represents an integer of 1 or more, Z represents the structural atom group which exists between two phosphorus atoms in the case where the phosphorus compound (B) has two or more phosphorus atoms in a molecule|numerator, , description of other substituents bonded to the phosphorus atom is omitted. In the layer (YA) of the multilayered structure of the present invention, one metal oxide (A) particle is bonded to a plurality of other metal oxide (A) particles from the viewpoint of gas barrier properties of the obtained multilayered structure. desirable.

The metal oxide (A) may be a hydrolysis-condensation product of a compound (L) containing a metal atom (M) to which a hydrolyzable characteristic group is bonded. Examples of the characteristic group include ^{X 1} of Formula II, which will be described later.

In addition, it is possible to consider that the hydrolysis-condensation product of compound (L) is a metal oxide substantially. For this reason, in this specification, the hydrolysis-condensation product of compound (L) may be called "metal oxide (A)." That is, in this specification, "metal oxide (A)" can be read interchangeably with "hydrolysis-condensation product of compound (L)", and "hydrolysis-condensation product of compound (L)" can be read as "metal oxide ( It is possible to read it as "A)".

[Metal Oxide (A)]

As a metal atom constituting the metal oxide (A) (these may be collectively referred to as "metal atom (M)"), a metal having a valence of divalent or higher (for example, 2 to tetravalent or 3 to tetravalent) and atoms, and specific examples thereof include metals of Group 2 in the periodic table such as magnesium and calcium; metals of Group 12 in the periodic table such as zinc; metals of Group 13 in the periodic table such as aluminum; metals of Group 14 of the periodic table such as silicon; Transition metals, such as titanium and zirconium, etc. are mentioned. In addition, although silicon may be classified as a semimetal, in this specification, silicon shall be included in a metal. The number of metal atoms (M) constituting the metal oxide (A) may be one or two or more, but it is necessary to contain at least aluminum. As the metal atom (M) that can be used in combination with aluminum, at least one selected from the group consisting of titanium and zirconium because of the ease of handling for producing the metal oxide (A) and excellent gas barrier properties of the resulting multilayer structure. It is preferably a species.

The total ratio of aluminum, titanium, and zirconium in the metal atom M may be 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 100 mol%. In addition, the ratio of aluminum to the metal atom M may be 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 100 mol%.

As the metal oxide (A), one produced by a method such as a liquid phase synthesis method, a gas phase synthesis method, or a solid pulverization method can be used. It is preferable that it is manufactured by a liquid phase synthesis method.

In the liquid phase synthesis method, a compound (L) in which a hydrolyzable characteristic group is bonded to a metal atom (M) is used as a raw material, and the metal oxide (A) is synthesized as a hydrolysis-condensation product of the compound (L) by hydrolytic condensation. can However, the metal atom (M) which the compound (L) has needs to contain aluminum at least. In the production of a hydrolysis-condensation product of compound (L) by a liquid phase synthesis method, in addition to a method using compound (L) itself as a raw material, partial hydrolysis of compound (L) formed by partial hydrolysis of compound (L) A hydrolyzate, a complete hydrolyzate of the compound (L) formed by complete hydrolysis of the compound (L), a partial hydrolysis-condensation product of a compound (L) formed by partially hydrolysis-condensing the compound (L), and complete hydrolysis of the compound (L) A metal oxide (A) can also be manufactured by using what condensed a part of hydrolyzate, or a mixture of 2 or more types of these as a raw material, and condensing or hydrolysis-condensing this. The metal oxide (A) obtained in this way is also referred to as "hydrolysis-condensation product of compound (L)" in this specification. There is no particular limitation on the type of the hydrolyzable characteristic group (functional group), for example, a halogen atom (F, Cl, Br, I, etc.), an alkoxy group, an acyloxy group, a diacylmethyl group, a nitro group, etc. However, since it is excellent in the controllability of reaction, a halogen atom or an alkoxy group is preferable, and an alkoxy group is more preferable.

The compound (L) preferably contains ^{at least one compound (L 1} ) represented by the following formula (II) because it is easy to control the reaction and has excellent gas barrier properties of the resulting multilayered structure.

Formula II

In the above formula (II),

X ¹ is selected from the group consisting of F, Cl, Br, I, R ² O-, R ³ C(=O)O-, (R ⁴ C(=O)) ₂ CH- and NO _{3 .} R ¹ , R ² , R ³ and R ⁴ are each selected from the group consisting of an alkyl group, an aralkyl group, an aryl group and an alkenyl group. In the general formula (II), when a plurality of X ^1s exist, these X ^1s may be the same as or different from each other. In general formula (II), when a plurality of R ¹ is present, these R ¹ may be the same as or different from each other. In the general formula (II), when a plurality of R ^{2 s} exist, these R ² may be the same as or different from each other. In formula (II), when a plurality of R ³ is present, these R ³ may be the same as or different from each other. In the general formula (II), when a plurality of R ⁴ is present, these R ⁴ may be the same as or different from each other. m represents the integer of 1-3.

Examples of the alkyl group represented by R ¹ , R ² , R ³ and R ⁴ include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, a s-butyl group, a t-butyl group, and 2-ethylhexyl group. and the like. Examples of the aralkyl group represented by R ¹ , R ² , R ³ and R ⁴ include a benzyl group, a phenethyl group, and a trityl group. Examples of the aryl group represented by R ¹ , R ² , R ³ and R ⁴ include a phenyl group, a naphthyl group, a tolyl group, a xylyl group, and a mesityl group. Examples of the alkenyl group represented by R ¹ , R ² , R ³ and R ⁴ include a vinyl group and an allyl group. It is preferable that it is a C1-C10 alkyl group, and, as for R<^1> , for example, it is more preferable that it is a C1-C4 alkyl group. X ¹ is preferably F, Cl, Br, I, R ^{2 O—.} In a preferred example of the compound (L ^{1 ), X 1} is a halogen atom (F, Cl, Br, I) or an alkoxy group having 1 to 4 carbon atoms (R ² O—), and m is 3. In an example of the compound (L ^{1 ), X 1} is a halogen atom (F, Cl, Br, I) or an alkoxy group having 1 to 4 carbon atoms (R ² O—), and m is 3.

Further, the compound (L) may contain at least one compound represented by the following formula (III) in addition to the ^{compound (L 1 ).}

[Formula III]

In the above formula (III),

M ¹ represents Ti or Zr. X ¹ is selected from the group consisting of F, Cl, Br, I, R ² O-, R ³ C(=O)O-, (R ⁴ C(=O)) ₂ CH- and NO _{3 .} R ¹ , R ² , R ³ and R ⁴ are each selected from the group consisting of an alkyl group, an aralkyl group, an aryl group and an alkenyl group. In the general formula (III), when a plurality of X ^1s exist, these X ^1s may be the same as or different from each other. In general formula (III), when a plurality of R ¹ is present, these R ¹ may be the same as or different from each other. In the formula (III), when a plurality of R ^{2 s} exist, these R ² may be the same as or different from each other. In the formula (III), when a plurality of R ³ is present, these R ³ may be the same as or different from each other. In the general formula (III), when a plurality of R ⁴ is present, these R ⁴ may be the same as or different from each other. n is equal to the valence ^{of M 1 .} m represents an integer of 1 to n.

Specific examples of the compound (L ¹ ) include aluminum chloride, aluminum triethoxide, aluminum trinormal propoxide, aluminum triisopropoxide, aluminum trinormal butoxide, aluminum tris-butoxide, aluminum and aluminum compounds such as trit-butoxide, aluminum triacetate, aluminum acetylacetonate, and aluminum nitrate. Among these, as the compound (L ¹ ), at least one compound selected from aluminum triisopropoxide and aluminum tris-butoxide is preferable. Compound (L ¹⁾ above may be used one kind alone or may be used in combination of two or more.

As long as the effect of the present invention is obtained ^{, the ratio of the compound (L 1} ) to the compound (L) is not particularly limited. The ratio for compounds other than the compound (L ¹ ) to the compound (L) is, for example, 20 mol% or less, 10 mol% or less, 5 mol% or less, or 0 mol%. In one example, compound (L) consists only ^{of compound (L 1 ).}

In addition, the compound (L ^{) other than the compound (L 1} ) is not particularly limited as long as the effect of the present invention is obtained. For example, to a metal atom such as titanium, zirconium, magnesium, calcium, zinc, or silicon, and compounds to which one hydrolyzable characteristic group is bonded. In addition, although silicon may be classified as a semimetal, in this specification, silicon shall be included in a metal. ^{Among these, as the compound (L) other than the compound (L 1} ), a compound having titanium or zirconium as a metal atom is preferable because the obtained multilayer structure has excellent gas barrier properties. Specific examples of the compound (L) other than the compound (L ¹ ) include, for example, titanium tetraisopropoxide, titanium tetranormal butoxide, titanium tetra(2-ethylhexoxide), titanium tetramethoxide, and titanium tetrae. titanium compounds such as a oxide and titanium acetylacetonate; and zirconium compounds such as zirconium tetranormal propoxide, zirconium tetrabutoxide, and zirconium tetraacetylacetonate.

When the compound (L) is hydrolyzed, at least a part of the hydrolyzable characteristic group of the compound (L) is substituted with a hydroxyl group. Further, when the hydrolyzate is condensed, a compound in which a metal atom (M) is bonded via an oxygen atom (O) is formed. If this condensation is repeated, a compound that can be considered substantially as a metal oxide is formed. In addition, a hydroxyl group exists normally on the surface of the metal oxide (A) formed in this way.

In this specification, the oxygen atom bonded only to the metal atom (M) like the oxygen atom (O) in the structure represented by MOM with respect to the number of moles of the metal atom (M) (for example, represented by MOH) The ratio of the number of moles ([Oxygen atom bonded only to the metal atom (M)] in the structure to be formed, excluding the oxygen atom bonded to the metal atom (M) and the hydrogen atom (H) like the oxygen atom (O) Let the metal oxide (A) contain a compound in which (the number of moles of (O)]/[the number of moles of metal atoms (M)]) is 0.8 or more. It is preferable that the said ratio is 0.9 or more, as for a metal oxide (A), It is more preferable that it is 1.0 or more, It is still more preferable that it is 1.1 or more. Although the upper limit of the said ratio is not specifically limited, When the valence of the metal atom (M) is set to n, it is normally represented by n/2.

In order for said hydrolysis-condensation to occur, it is important that compound (L) has a hydrolyzable characteristic group (functional group). When these groups are not couple|bonded, since a hydrolysis-condensation reaction does not occur or it becomes very slow, preparation of the target metal oxide (A) becomes difficult.

A hydrolysis-condensation product can be manufactured from a specific raw material by the method employ|adopted by the well-known sol-gel method, for example. The raw material contains a part of compound (L), a partial hydrolyzate of compound (L), a complete hydrolyzate of compound (L), a partial hydrolysis-condensation product of compound (L), and a part of a complete hydrolyzate of compound (L). At least one selected from the group consisting of condensed substances (hereinafter, sometimes referred to as "compound (L)-based component") can be used. These raw materials may be manufactured by a well-known method, and a commercially available thing may be used for it. Although there is no restriction|limiting in particular, For example, the condensate obtained by hydrolytic-condensation of about 2-10 compounds (L) can be used as a raw material. Specifically, for example, aluminum triisopropoxide can be hydrolyzed and condensed to form a condensate of 2 to 10 mers, which can be used as a part of the raw material.

The number of molecules to be condensed in the hydrolysis-condensation product of the compound (L) can be controlled by the conditions at the time of condensation or hydrolysis-condensation of the compound (L)-based component. For example, the number of molecules to be condensed can be controlled by the amount of water, the type or concentration of the catalyst, the temperature or time for condensation or hydrolysis condensation, and the like.

As described above, the layer (YA) included in the multilayered structure of the present invention contains a reaction product (R), and the reaction product (R) is a metal oxide (A) containing at least aluminum and a phosphorus compound (B). ) is a product of the reaction. Such a reaction product can be formed by mixing and reacting a metal oxide (A) and a phosphorus compound (B). The metal oxide (A) used for mixing with the phosphorus compound (B) (immediately before mixing) may be the metal oxide (A) itself, or may be in the form of a composition containing the metal oxide (A). In a preferred example, the metal oxide (A) is mixed with the phosphorus compound (B) in the form of a liquid (solution or dispersion) obtained by dissolving or dispersing the metal oxide (A) in a solvent.

A preferred method for preparing a solution or dispersion of the metal oxide (A) is described below. Here, a method for preparing the dispersion will be described taking as an example the case where the metal oxide (A) contains no metal atoms other than aluminum atoms, that is, the case where the metal oxide (A) is aluminum oxide (alumina), but other metal atoms A similar preparation method can be employed when preparing a solution or dispersion containing A preferable dispersion of alumina can be obtained by hydrolytically condensing aluminum alkoxide in an aqueous solution whose pH is adjusted with an acid catalyst as necessary to obtain an alumina slurry, which is then peptized in the presence of a specific amount of acid.

The temperature of the reaction system at the time of hydrolysis-condensing an aluminum alkoxide is not specifically limited. The temperature of the said reaction system exists in the range of 2-100 degreeC normally. When water and aluminum alkoxide come into contact, the temperature of the liquid rises, but alcohol is produced as a by-product as the hydrolysis proceeds, and when the boiling point of the alcohol is lower than that of water, the alcohol volatilizes so that the temperature of the reaction system is higher than near the boiling point of the alcohol. may not rise. In such a case, since the growth of alumina may become slow, it is effective to remove the alcohol by heating to around 95°C. The reaction time varies depending on the reaction conditions (the presence or absence of an acid catalyst, the amount or type, etc.). The reaction time is usually in the range of 0.01 to 60 hours, preferably in the range of 0.1 to 12 hours, and more preferably in the range of 0.5 to 6 hours. In addition, the reaction can be performed in the atmosphere of various gases, such as air, carbon dioxide, nitrogen, and argon.

It is preferable that it is 1-200 mol times with respect to aluminum alkoxide, and, as for the quantity of the water used at the time of hydrolysis condensation, it is more preferable that it is 10-100 mol times. When the amount of water is less than 1 mole times, it is not preferable because hydrolysis does not proceed sufficiently. On the other hand, when it exceeds 200 molar times, since manufacturing efficiency falls or a viscosity becomes high, it is unpreferable. When using a component containing water (for example, hydrochloric acid or nitric acid), it is preferable to determine the amount of water used in consideration of the amount of water introduced according to the component.

As an acid catalyst used for hydrolysis condensation, hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid, benzoic acid, acetic acid, lactic acid, butyric acid, carbonic acid, oxalic acid, maleic acid, etc. can be used. Among these, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, lactic acid, and butyric acid are preferable, and nitric acid and acetic acid are more preferable. When using an acid catalyst at the time of hydrolysis-condensation, it is preferable to use the suitable amount according to the kind of acid so that the pH before hydrolysis-condensation may be in the range of 2.0-4.0.

Although the slurry of alumina obtained by hydrolysis condensation may be used as it is as an alumina dispersion, by heating and peptizing the slurry of alumina obtained in the presence of a specific amount of acid, a dispersion of transparent and excellent viscosity stability can be obtained. can

Monovalent inorganic acids and organic acids, such as nitric acid, hydrochloric acid, perchloric acid, formic acid, acetic acid, and propionic acid, can be used as an acid used at the time of peptization. Among these, nitric acid, hydrochloric acid, and acetic acid are preferable, and nitric acid and acetic acid are more preferable.

When nitric acid or hydrochloric acid is used as the acid for peptization, the amount is preferably 0.001 to 0.4 mole times, more preferably 0.005 to 0.3 mole times, relative to the aluminum atom. In the case of less than 0.001 mole times, peptization may not proceed sufficiently, or a problem may occur, such as requiring a very long time. Moreover, when it exceeds 0.4 molar times, the stability with time of the dispersion of alumina obtained tends to fall.

On the other hand, when acetic acid is used as the acid at the time of peptization, the amount is preferably 0.01 to 1.0 mole times, more preferably 0.05 to 0.5 mole times relative to the aluminum atom. In the case of less than 0.01 mole times, peptization may not proceed sufficiently, or a problem such as requiring a very long time may occur. Moreover, when it exceeds 1.0 molar times, the stability with time of the dispersion of alumina obtained tends to fall.

The acid present at the time of peptization may be added at the time of hydrolysis condensation, but when the acid is lost when the alcohol by-product in hydrolysis condensation is removed, it is preferable to add it again so that it may become an amount within the above range.

By carrying out the peptization within the range of 40 to 200°C, the dispersion of alumina having a predetermined particle size and excellent viscosity stability can be prepared by peptizing in a short time with an appropriate amount of acid. If the temperature at the time of peptization is less than 40°C, it requires a long time for peptization, and when it exceeds 200°C, the increase in the peptization rate by raising the temperature is weak, while it is economically disadvantageous because it requires a high pressure vessel, etc. It is not advisable because

After peptization is completed, a dispersion of alumina having a predetermined concentration can be obtained by diluting with a solvent or concentrating by heating if necessary. However, in order to suppress thickening or gelation, when heat-concentrating, it is preferable to carry out under reduced pressure at 60 degrees C or less.

It is preferable that the metal oxide (A) provided for mixing with a phosphorus compound (B) (a composition containing a phosphorus compound (B) when used as a composition) contains substantially no phosphorus atom. However, for example, due to the influence of impurities in the preparation of the metal oxide (A), etc., it is used for mixing with the phosphorus compound (B) (when used as a composition, the composition containing the phosphorus compound (B)). A small amount of phosphorus atoms may be mixed in the used metal oxide (A). For this reason, within the range in which the effect of this invention is not impaired, the metal oxide (A) provided for mixing with a phosphorus compound (B) (a composition containing a phosphorus compound (B) when used as a composition) is small may contain a phosphorus atom of The content rate of phosphorus atoms contained in the metal oxide (A) used for mixing with the phosphorus compound (B) (a composition containing the phosphorus compound (B) when used as a composition) is a multilayered structure having more excellent gas barrier properties. is obtained, based on (100 mol%) the number of moles of all metal atoms (M) contained in the metal oxide (A), preferably 30 mol% or less, more preferably 10 mol% or less, 5 It is more preferable that it is mol% or less, and it is especially preferable that it is 1 mol% or less, and 0 mol% may be sufficient.

In the layer (YA) which the multilayer structure of the present invention has, the particles of the metal oxide (A) have a specific structure bonded through a phosphorus atom derived from the phosphorus compound (B), but in the layer (YA) Particles of metal oxide (A) provided for mixing with the shape and size of the particles of the metal oxide (A) in the composition, and the phosphorus compound (B) (composition containing the phosphorus compound (B) when used as a composition) The shape and size of may be the same or different, respectively. That is, the particle|grains of the metal oxide (A) used as a raw material of the layer (YA) may change in shape and size in the process of forming the layer (YA). In particular, when forming the layer (YA) using the coating liquid (U) described later, in the coating liquid (U) or in the liquid (S) described later that can be used to form it, or the coating liquid (U) is applied to the substrate ( X) Each process after application|coating on the WHEREIN: A shape and a size may change.

[phosphorus compound (B)]

The phosphorus compound (B) contains a site capable of reacting with the metal oxide (A), and typically contains a plurality of such sites. In a preferred example, the phosphorus compound (B) contains 2 to 20 such sites (atomic groups or functional groups). Examples of such a site include a site capable of reacting with a functional group (for example, a hydroxyl group) present on the surface of the metal oxide (A). For example, examples of such a moiety include a halogen atom directly bonded to a phosphorus atom and an oxygen atom directly bonded to a phosphorus atom. These halogen atoms and oxygen atoms can cause a condensation reaction (hydrolysis condensation reaction) with a hydroxyl group present on the surface of the metal oxide (A). The functional group (for example, hydroxyl group) which exists on the surface of the metal oxide (A) is couple|bonded with the metal atom (M) which comprises the metal oxide (A) normally.

As the phosphorus compound (B), for example, one having a structure in which a halogen atom or an oxygen atom is directly bonded to a phosphorus atom can be used, and by using such a phosphorus compound (B), a hydroxyl group present on the surface of the metal oxide (A) (hydrolysis) It can couple|bond by condensing. The phosphorus compound (B) may have one phosphorus atom or may have two or more phosphorus atoms.

The phosphorus compound (B) may be at least one compound selected from the group consisting of phosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid, and derivatives thereof. Specific examples of polyphosphoric acid include polyphosphoric acid in which pyrophosphoric acid, triphosphate, and four or more phosphoric acids are condensed. Examples of the above derivatives include phosphoric acid, polyphosphoric acid, phosphorous acid, and phosphonic acid, salts, (partial) ester compounds, halides (chlorides, etc.), and dehydrates (diphosphorus pentoxide, etc.). In addition, examples of the derivative of phosphonic acid include _{a compound in which a hydrogen atom directly bonded to a phosphorus atom of phosphonic acid (HP(=O)(OH) 2} ) is substituted with an alkyl group which may have various functional groups (e.g., nitrile tris(methylenephosphonic acid), N,N,N',N'-ethylenediaminetetrakis(methylenephosphonic acid) and the like), salts thereof, (partial) ester compounds, halides and dehydrated products are also included. In addition, an organic polymer having a phosphorus atom, such as phosphorylated starch or a polymer (E) described later, can also be used as the phosphorus compound (B). These phosphorus compounds (B) may be used individually by 1 type, or may use 2 or more types together. Among these phosphorus compounds (B), when the layer (YA) is formed using the coating solution (U) described later, the stability of the coating solution (U) and the gas barrier properties of the resulting multilayer structure are more excellent, so phosphoric acid It is preferable to use independently, or to use phosphoric acid and a phosphorus compound other than that together.

As described above, the layer (YA) of the multilayer structure of the present invention contains a reaction product (R), and the reaction product (R) is at least a metal oxide (A) and a phosphorus compound (B) react It is a reaction product that consists of Such a reaction product can be formed by mixing and reacting a metal oxide (A) and a phosphorus compound (B). The phosphorus compound (B) provided for mixing with the metal oxide (A) (just before mixing) may be in the form of a phosphorus compound (B) itself or a composition containing a phosphorus compound (B), or a phosphorus compound ( The form of the composition containing B) is preferred. In a preferred example, the phosphorus compound (B) is mixed with the metal oxide (A) in the form of a solution obtained by dissolving the phosphorus compound (B) in a solvent. Although arbitrary solvents can be used for the solvent in that case, water or the mixed solvent containing water is mentioned as a preferable solvent.

In the composition containing the phosphorus compound (B) or the phosphorus compound (B) to be mixed with the metal oxide (A), it is preferable that the content of metal atoms is low because a multilayered structure having better gas barrier properties can be obtained. The content rate of the metal atom contained in the composition containing the phosphorus compound (B) or the phosphorus compound (B) to be mixed with the metal oxide (A) is, Based on the number of moles of all phosphorus atoms contained in the composition as a standard (100 mol%), it is preferably 100 mol% or less, more preferably 30 mol% or less, still more preferably 5 mol% or less, and 1 mol% or less It is especially preferable, and 0 mol% may be sufficient.

[reaction product (R)]

The reaction product (R) contains a reaction product produced when only the metal oxide (A) and the phosphorus compound (B) react. Further, the reaction product (R) also contains a reaction product formed by reacting the metal oxide (A), the phosphorus compound (B), and another compound. A reaction product (R) can be formed by the method demonstrated by the manufacturing method mentioned later.

[Ratio of metal oxide (A) and phosphorus compound (B)]

In the layer (YA), the number of moles (N _{M ) of metal atoms constituting the metal oxide (A) and the number of moles (N P} ) of phosphorus atoms derived from the phosphorus compound (B) are 1.0≤ (number of moles (N _M ) ) / (mol number (N _P)), it is preferable to satisfy the relationship of ≤3.6, 1.1≤ (molar number (N _M)) / (molar number (N _P)), it is more preferable to satisfy the relationship of ≤3.0. When the value of (number of moles (N _M ))/(number of moles ( _NP )) exceeds 3.6, the metal oxide (A) becomes excessive with respect to the phosphorus compound (B), and the bonding between the particles of the metal oxide (A) is Since it becomes insufficient and the quantity of the hydroxyl group which exists on the surface of a metal oxide (A) increases, there exists a tendency for gas barrier property and the stability to fall. On the other hand, when the value of (number of moles (N _M ))/(number of moles ( _NP )) is less than 1.0, the phosphorus compound (B) becomes excessive with respect to the metal oxide (A), and is involved in bonding with the metal oxide (A) The excess phosphorus compound (B) which is not formed increases, and the quantity of the hydroxyl group derived from a phosphorus compound (B) increases easily, and there exists a tendency for gas-barrier property and the stability to fall, too.

In addition, the said ratio can be adjusted with the ratio of the quantity of the metal oxide (A) and the quantity of the phosphorus compound (B) in the coating liquid for forming the layer (YA). Configuring the number of moles (N _M) and the molar number (N _P) ratio is usually, as the ratio of the coating solution the metal oxide (A) of the mole number of the metal atoms and constituting the compound of (B) in the layer (YA) equal to the ratio of moles of phosphorus atoms.

[Polymer (C)]

The layer (YA) included in the multilayered structure of the present invention may further contain a specific polymer (C). The polymer (C) is a polymer having at least one functional group (f) selected from the group consisting of a hydroxyl group, a carboxyl group, a carboxylic acid anhydride group, and a salt of a carboxyl group. In the layer (YA) of the multilayer structure, the polymer (C) is directly or both with one or both of the particles of the metal oxide (A) and the phosphorus atom derived from the phosphorus compound (B) by the functional group (f) it has. You may couple indirectly. In addition, in the layer (YA) of the multilayer structure, the reaction product (R) may have a portion of the polymer (C) produced by reacting the polymer (C) with the metal oxide (A) or the phosphorus compound (B). . In addition, in this specification, the polymer containing a functional group (f) as a polymer which satisfy|fills the requirements as a phosphorus compound (B) is not included in a polymer (C), but is handled as a phosphorus compound (B).

As a polymer (C), the polymer containing the structural unit which has a functional group (f) can be used. Specific examples of such a structural unit include a structural unit having at least one functional group (f), such as a vinyl alcohol unit, an acrylic acid unit, a methacrylic acid unit, a maleic acid unit, an itaconic acid unit, a maleic anhydride unit, and a phthalic anhydride unit. can be heard The polymer (C) may contain one type of structural unit which has a functional group (f), and may contain two or more types of structural units which have a functional group (f).

In order to obtain a multilayered structure having more excellent gas barrier properties and stability thereof, the proportion of the structural units having a functional group (f) to all the structural units of the polymer (C) is preferably 10 mol% or more, and 20 mol % or more, more preferably 40 mol% or more, particularly preferably 70 mol% or more, and may be 100 mol%.

When a polymer (C) is comprised by the structural unit which has a functional group (f), and other structural units other than that, the kind of the said other structural unit is not specifically limited. Examples of the other structural units include structural units derived from (meth)acrylic acid esters such as methyl acrylate units, methyl methacrylate units, ethyl acrylate units, ethyl methacrylate units, butyl acrylate units, and butyl methacrylate units. ; structural units derived from vinyl esters such as vinyl formate units and vinyl acetate units; structural units derived from aromatic vinyl such as styrene units and p-styrenesulfonic acid units; and structural units derived from olefins such as ethylene units, propylene units, and isobutylene units. When the polymer (C) contains two or more types of structural units, the polymer (C) may be any of an alternating copolymer, a random copolymer, a block copolymer, and a tapered copolymer.

Specific examples of the polymer (C) having a hydroxyl group include polyvinyl alcohol, partially saponified polyvinyl acetate, polyethylene glycol, polyhydroxyethyl (meth)acrylate, polysaccharides such as starch, and polysaccharide derivatives derived from polysaccharides. can Specific examples of the polymer (C) having a carboxyl group, a carboxylic acid anhydride group or a salt of a carboxyl group include polyacrylic acid, polymethacrylic acid, poly(acrylic acid/methacrylic acid) and salts thereof. Moreover, as a specific example of the polymer (C) containing the structural unit which does not contain a functional group (f), ethylene-vinyl alcohol copolymer, ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, isobutylene- The saponified material of maleic anhydride alternating copolymer, an ethylene-acrylic acid copolymer, and an ethylene-ethyl acrylate copolymer, etc. are mentioned. In order to obtain a multilayered structure having better gas barrier properties and stability thereof, the polymer (C) is polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polysaccharide, polyacrylic acid, a salt of polyacrylic acid, polymethacrylic acid, and It is preferable that it is at least 1 sort(s) of polymer selected from the group which consists of salts of polymethacrylic acid.

There is no restriction|limiting in particular in the molecular weight of polymer (C). In order to obtain a multilayer structure having more excellent gas barrier properties and mechanical properties (drop impact strength, etc.), the number average molecular weight of the polymer (C) is preferably 5,000 or more, more preferably 8,000 or more, and further preferably 10,000 or more. desirable. The upper limit of the number average molecular weight of a polymer (C) is not specifically limited, For example, it is 1,500,000 or less.

In order to further improve gas barrier properties, the content rate of the polymer (C) in the layer (YA) is preferably 50 mass% or less on the basis of the mass of the layer (YA) (100 mass%), and 40 mass% % or less, more preferably 30 mass % or less, and may be 20 mass % or less. The polymer (C) may or may not react with the other component in the layer (YA). In addition, in this specification, also when a polymer (C) is reacting with another component, it expresses as a polymer (C). For example, also when the polymer (C) is couple|bonded with the phosphorus atom derived from a metal oxide (A) and/or a phosphorus compound (B), it expresses as a polymer (C). In this case, the content rate of said polymer (C) is calculated by dividing the mass of the polymer (C) before bonding to the metal oxide (A) and/or the phosphorus atom by the mass of the layer (YA).

The layer (YA) included in the multilayer structure contains at least a reaction product (R) formed by reacting a metal oxide (A) containing aluminum and a phosphorus compound (B) (provided that only those having a polymer (C) moiety are included) only. It may be comprised, and although it may be comprised only from the said reaction product (R) and the polymer (C) which has not reacted, you may contain other components further.

As said other component, For example, inorganic acid metal salts, such as carbonate, hydrochloride, nitrate, hydrogencarbonate, sulfate, hydrogensulfate, a borate, and an aluminate; organic acid metal salts such as oxalate, acetate, tartrate and stearate; Metal complexes, such as an acetylacetonate metal complex (aluminum acetylacetonate etc.), a cyclopentadienyl metal complex (titanocene etc.), and a cyano metal complex; layered clay compounds; crosslinking agent; high molecular compounds other than the polymer (C); plasticizer; antioxidants; UV absorbers; A flame retardant etc. are mentioned.

The content rate of the above-mentioned other components in the layer (YA) in the multilayer structure is preferably 50 mass% or less, more preferably 20 mass% or less, still more preferably 10 mass% or less, and particularly that it is 5 mass% or less Preferably, 0 mass % (no other component is contained) may be sufficient.

[Thickness of layer (YA)]

The thickness of the layer (YA) of the multilayer structure of the present invention (the sum of the thicknesses of each layer (YA) when the multilayer structure has two or more layers (YA)) is preferably 4.0 µm or less, and 2.0 µm or less It is more preferable, and it is still more preferable that it is 1.0 micrometer or less, and 0.9 micrometer or less may be sufficient. By making the layer (YA) thin, the dimensional change of the multilayer structure during processing such as printing and lamination can be suppressed to a low level, and the flexibility of the multilayer structure is increased, and its mechanical properties are reflected in the mechanical properties of the substrate itself. can be close

In the multilayer structure of the present invention, even when the total thickness of the layers (YA) is 1.0 µm or less (for example, 0.5 µm or less), the oxygen permeability under the conditions of 20°C and 85%RH is 2 ml/(m 2 · day atm) or less. In addition, it is preferable that the thickness of the layer (YA) (the sum of the thicknesses of each layer (YA) when the multilayer structure has two or more layers (YA)) is 0.1 µm or more (for example, 0.2 µm or more) . Moreover, it is preferable that the thickness per layer of layer (YA) is 0.05 micrometer or more (for example, 0.15 micrometer or more) from a viewpoint that the gas barrier property of the multilayer structure of this invention becomes more favorable. The thickness of the layer YA can be controlled by the concentration of the coating liquid U, which will be described later, used for the formation of the layer YA, and the application method thereof.

[Floor (YB) and Floor (YC)]

The layer (Y) included in the multilayer structure of the present invention may be a layer (YB) that is a vapor deposition layer of aluminum or a layer (YC) that is a vapor deposition layer of aluminum oxide. These vapor deposition layers can be manufactured by the method similar to the inorganic vapor deposition layer mentioned later.

[Layer (Z)]

The layer (Z) included in the multilayered structure of the present invention contains a polymer (E) having a plurality of phosphorus atoms. By forming the layer (Z) adjacent to the layer (Y), the bending resistance of the multilayer structure of the present invention can be significantly improved.

[Polymer (E)]

The polymer (E) has a plurality of phosphorus atoms in the polymer. In one example, the said phosphorus atom is contained in an acidic group or its derivative(s). Examples of the acidic group containing a phosphorus atom include a phosphoric acid group, a polyphosphoric acid group, a phosphorous acid group, and a phosphonic acid group. Among the plurality of phosphorus atoms that the polymer (E) has, at least one phosphorus atom contains a site capable of reacting with the metal oxide (A). In a preferable example, the polymer (E) contains about 10 to 1000 such phosphorus atoms. As an example of the site|part regarding the phosphorus atom which can react with a metal oxide (A), the site|part of the structure described with respect to the phosphorus compound (B) is mentioned.

The polymer (E) is not particularly limited as long as the above conditions are satisfied, and preferred examples thereof include homopolymers or copolymers of vinylphosphonic acids containing a phosphoric acid group. Here, "vinylphosphonic acids" means satisfying the following requirements.

(a) phosphonic acid having a substituent, phosphinic acid having a substituent, or an ester thereof.

(b) The carbon chain of the substituent is bonded to the phosphorus atom in the molecule (the phosphorus atom in the phosphonic acid group, the phosphinic acid group, or the ester thereof) through a phosphorus-carbon bond. A carbon-carbon double bond is present in the carbon chain. A part of the carbon chain may constitute a carbon ring.

(c) At least 1 hydroxyl group is couple|bonded with the phosphorus atom (phosphorus atom in a phosphonic acid group, a phosphinic acid group, or these ester) in a molecule|numerator.

Examples of vinylphosphonic acids are phosphonic acids and/or phosphinic acids having a substituent, and satisfy the requirements of (b) above. For example, an example of phosphonic acids is a phosphonic acid having a substituent and satisfies the requirement of (b) above.

The carbon number contained in the carbon chain of the substituent couple|bonded with the phosphorus atom may be in the range of 2-30 (for example, the range of 2-10). Examples of the substituent include a hydrocarbon chain having a carbon-carbon double bond (eg, vinyl group, allyl group, 1-propenyl group, isopropenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group) phenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group, 1-hexenyl group, 1,3-hexadienyl group, 1,5-hexadienyl group, etc.). The hydrocarbon chain having a carbon-carbon double bond may contain one or more oxycarbonyl groups in the molecular chain. Examples of the carbon ring include a benzene ring, a naphthalene ring, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclopropene ring, a cyclobutene ring, a cyclopentene ring, and the like. In addition to the hydrocarbon chain having a carbon-carbon double bond on the carbon ring, one or more saturated hydrocarbon chains (eg, methyl group, ethyl group, propyl group, etc.) may be bonded. Examples of the substituent bonded to the phosphorus atom include a hydrocarbon chain having the carbon-carbon double bond such as a vinyl group, and a carbon ring in which the hydrocarbon chain is bonded to the carbon ring such as a 4-vinylbenzyl group.

The ester group constituting the ester has a structure in which a hydrogen atom of a hydroxyl group bonded to a phosphorus atom of phosphinic acid or phosphonic acid is substituted with an alkyl group, and the alkyl group includes, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, A hexyl group etc. are mentioned.

The polymer (E) can be obtained by polymerizing a vinyl phosphonic acid monomer or copolymerizing it with another vinyl group-containing monomer. The polymer (E) can also be obtained by hydrolyzing a phosphonic acid halide or vinylphosphonic acid derivative such as an ester, alone or after copolymerization.

Examples of the vinylphosphonic acid monomer that can be suitably used in the present invention include alkenylphosphonic acids such as vinylphosphonic acid and 2-propene-1-phosphonic acid; alkenyl aromatic phosphonic acids such as 4-vinylbenzyl phosphonic acid and 4-vinylphenyl phosphonic acid; phosphono (methacrylate) such as 6-[(2-phosphonoacetyl)oxy]hexyl acrylate, phosphonomethyl methacrylate, 11-phosphonoundecyl methacrylate, and 1,1-diphosphonoethyl methacrylate ) acrylic acid esters; Phosphinic acids, such as vinyl phosphinic acid and 4-vinyl benzyl phosphinic acid, etc. are mentioned. Among them, polyvinylphosphonic acid, which is a homopolymer of vinylphosphonic acid, is more preferable from the viewpoint of obtaining a multilayered structure excellent in bending resistance. However, the monomers that can be used in the present invention are not limited thereto.

The polymer (E) of the present invention may be a homopolymer of the above-mentioned vinylphosphonic acid monomer, or a copolymer using two or more types of the above-mentioned vinylphosphonic acid monomer, or at least one type of the above-mentioned vinylphosphonic acid monomer. and a copolymer of another vinyl monomer.

The other vinyl monomer copolymerizable with the vinyl phosphonic acid monomer is not particularly limited as long as it can be copolymerized with the vinyl phosphonic acid monomer, and a known one can be used. As such a vinyl monomer, for example, acrylic acid, acrylic acid esters, methacrylic acid, methacrylic acid esters, acrylonitrile, methacrylonitrile, styrene, nuclear substituted styrenes, alkyl vinyl ethers, alkyl vinyl esters , perfluoro/alkyl vinyl ethers, perfluoro/alkyl vinyl esters, maleic acid, maleic anhydride, fumaric acid, itaconic acid, maleimide or phenylmaleimide. Among these vinyl monomers, methacrylic acid esters, acrylonitrile, styrenes, maleimides, and phenylmaleimides are particularly preferably used.

In order to obtain a multilayered structure having more excellent bending resistance, the ratio of the structural units derived from the monomers of the vinylphosphonic acids to all the structural units of the polymer (E) is preferably 10 mol% or more, and 20 mol % or more, more preferably 40 mol% or more, particularly preferably 70 mol% or more, and may be 100 mol%.

Although there is no restriction|limiting in particular in the molecular weight of polymer (E), Typically, the number average molecular weight of polymer (E) exists in the range of 1,000-100,000. When the number average molecular weight is within this range, the effect of improving the bending resistance by laminating the layer (Z) and the viscosity stability of the coating solution (V) containing the polymer (E) described later can be achieved at a high level. . Moreover, when the molecular weight of the polymer (E) per phosphorus atom exists in the range of 100-500, the improvement effect of the bending resistance by laminating|stacking the layer (Z) may be heightened more.

The polymer (E) may be polyvinylphosphonic acid represented by the following formula (I).

Formula I

In the above formula (I),

n is a natural number.

There is no particular limitation on n. n is, for example, a number satisfying the above-described number average molecular weight.

The layer (Z) included in the multilayered structure may be composed of only the polymer (E) having a plurality of phosphorus atoms, but may further contain other components.

As said other component, For example, inorganic acid metal salts, such as carbonate, hydrochloride, nitrate, hydrogencarbonate, sulfate, hydrogensulfate, and a borate; organic acid metal salts such as oxalate, acetate, tartrate and stearate; Metal complexes, such as an acetylacetonate metal complex (magnesium acetylacetonate etc.), a cyclopentadienyl metal complex (titanocene etc.), and a cyano metal complex; layered clay compounds; crosslinking agent; high molecular compounds other than the polymer (E); plasticizer; antioxidants; UV absorbers; A flame retardant etc. are mentioned.

The content of the above other components in the layer (Z) in the multilayer structure is preferably 50 mass % or less, more preferably 20 mass % or less, still more preferably 10 mass % or less, and particularly 5 mass % or less Preferably, 0 mass % (no other component is contained) may be sufficient.

The polymerization reaction for forming a polymer (E) can be performed using a polymerization initiator in the solvent in which both the monomer component used as a raw material, and the produced|generated polymer melt|dissolve. Examples of the polymerization initiator include 2,2-azobisisobutyronitrile, 2,2-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2-azobis(2-methylpropionate), Azo initiators such as dimethyl 2,2-azobisisobutylate and 2,2'-azobis(2-amidinopropane) dihydrochloride, lauryl peroxide, benzoyl peroxide, tert-butyl peroctoate, etc. Peroxide-based initiators and the like are included. In the case of copolymerization with other vinyl monomers, the solvent is appropriately selected according to the combination of the comonomers. You may use 2 or more types of mixed solvents as needed.

An exemplary polymerization reaction is carried out at a polymerization temperature of 50 to 100 ° C. while dropping a mixed solution consisting of a monomer, a polymerization initiator, and a solvent to the solvent, and maintained at a polymerization temperature or higher for about 1 to 24 hours after the completion of the dropping, Stirring is continued to complete polymerization.

When the monomer component is 1, the solvent is preferably used in a weight ratio of 0.1 to 3.0, and the polymerization initiator is preferably used in a weight ratio of 0.001 to 0.05. A more preferred weight ratio is 0.1 to 2.5 of the solvent. If the usage-amount of a solvent and a polymerization initiator is not in the said range, a problem may arise, such as a polymer gelatinizing and becoming insoluble in various solvents, and application|coating using a solution becomes impossible.

The layer (Z) included in the multilayered structure of the present invention can be formed by applying a solution of the polymer (E). Although arbitrary solvents can be used for the solvent in that case, water, alcohol, or these mixed solvents are mentioned as a preferable solvent.

[Thickness of Layer (Z)]

The thickness per layer of the layer (Z) is preferably 0.005 µm or more from the viewpoint of further improving the bending resistance of the multilayer structure of the present invention. Although the upper limit of the thickness of layer (Z) is not specifically limited, Since the effect of improving bending resistance reaches saturation at 1.0 micrometer or more, it is economically preferable to set the upper limit of the thickness of layer (Z) to 1.0 micrometer. The thickness of the layer (Z) can be controlled by the concentration of the coating solution (V) to be described later used for the formation of the layer (Z) and the application method thereof.

[Subscription (X)]

The material of the substrate (X) of the multilayer structure of the present invention is not particularly limited, and substrates made of various materials can be used. As a material of the base material (X), For example, resin, such as a thermoplastic resin and a thermosetting resin; fiber aggregates such as fabric and paper; wood; glass; metal; A metal oxide etc. are mentioned. Moreover, the thing of the composite structure which consists of several materials or the thing of a multilayer structure may be sufficient as a base material.

The shape of the substrate (X) is not particularly limited, and may be a layered substrate such as a film or a sheet, or various molded articles having a three-dimensional shape such as a sphere, a polyhedron, and a pipe. Among these, a layered base material is especially useful when using a multilayer structure (laminated structure) for a packaging material for packaging foodstuff etc., a solar cell member, etc.

The layered substrate is, for example, at least selected from the group consisting of a thermoplastic resin film layer, a thermosetting resin film layer, a fibrous polymer sheet (cloth, paper, etc.) layer, a wood sheet layer, a glass layer, an inorganic vapor deposition layer, and a metal foil layer. A single-layered or multi-layered substrate containing one type of layer can be exemplified. Among these, a substrate including at least one layer selected from the group consisting of a thermoplastic resin film layer, a paper layer and an inorganic vapor deposition layer is preferable, and the substrate in this case may be a single layer or a multilayer. A multilayer structure (laminated structure) using such a base material is excellent in processability into a packaging material and various properties required when used as a packaging material.

As a thermoplastic resin film which forms a thermoplastic resin film layer, For example, Polyolefin resins, such as polyethylene and a polypropylene; polyester resins such as polyethylene terephthalate, polyethylene-2,6-naphthalate, polybutylene terephthalate and copolymers thereof; polyamide-based resins such as nylon-6, nylon-66, and nylon-12; hydroxyl group-containing polymers such as polyvinyl alcohol and ethylene-vinyl alcohol copolymer; polystyrene; poly(meth)acrylic acid esters; polyacrylonitrile; polyvinyl acetate; polycarbonate; polyarylate; regenerated cellulose; polyimide; polyetherimide; polysulfone; polyethersulfone; polyether ether ketone; and a film obtained by molding a thermoplastic resin such as an ionomer resin. As the base material of the laminate used for a packaging material for packaging food or the like, a film made of polyethylene, polypropylene, polyethylene terephthalate, nylon-6, or nylon-66 is preferable.

A stretched film may be sufficient as a thermoplastic resin film, and an unstretched film may be sufficient as it. A stretched film, particularly a biaxially stretched film, is preferable because the resulting multilayered structure has excellent processing aptitude (printing, lamination, etc.). The biaxially stretched film may be a biaxially stretched film produced by any one of a simultaneous biaxial stretching method, a sequential biaxial stretching method, and a tubular stretching method.

Examples of the paper used for the paper layer include kraft paper, fine paper, imitation paper, glassine paper, partition paper, synthetic paper, white cardboard, manila ball, milk carton base paper, cup base paper, and ivory paper. By using a substrate including a paper layer, a multilayered structure for a paper container can be obtained.

It is preferable that an inorganic vapor deposition layer has barrier property with respect to oxygen gas or water vapor|steam. As an inorganic vapor deposition layer, what has light-shielding property like metal vapor deposition layers, such as aluminum, and what has transparency can be used suitably. An inorganic vapor deposition layer can be formed by vapor-depositing an inorganic substance on a base|substrate, and the whole laminated body in which the inorganic vapor deposition layer was formed on the base|substrate can be used as base material X of a multilayer structure. As an inorganic vapor deposition layer which has transparency, For example, a layer formed from inorganic oxides, such as aluminum oxide, a silicon oxide, a silicon oxynitride, magnesium oxide, a tin oxide, or a mixture thereof; a layer formed of an inorganic nitride such as silicon nitride or silicon carbonitride; and a layer formed of an inorganic carbide such as silicon carbide. Among these, the layer formed of aluminum oxide, silicon oxide, magnesium oxide, and silicon nitride is preferable from a viewpoint of being excellent in the barrier property with respect to oxygen gas and water vapor|steam.

Although the preferable thickness of an inorganic vapor deposition layer changes with the kind of component which comprises an inorganic vapor deposition layer, it exists in the range of 2-500 nm normally. Within this range, it is sufficient to select a thickness at which the barrier properties and mechanical properties of the multilayer structure are satisfactory. When the thickness of the inorganic vapor deposition layer is less than 2 nm, the reproducibility of the barrier property expression of the inorganic vapor deposition layer to oxygen gas or water vapor tends to decrease, and the inorganic vapor deposition layer may not exhibit sufficient barrier properties. Moreover, when the thickness of an inorganic vapor deposition layer exceeds 500 nm, when a multilayer structure is pulled or bent, there exists a tendency for the barrier property of an inorganic vapor deposition layer to fall easily. The thickness of an inorganic vapor deposition layer becomes like this. More preferably, it exists in the range of 5-200 nm, More preferably, it exists in the range of 10-100 nm.

Examples of the method for forming the inorganic vapor deposition layer include a vacuum deposition method, a sputtering method, an ion plating method, and a chemical vapor deposition method (CVD). Among these, the vacuum vapor deposition method is preferable from a viewpoint of productivity. As a heating method at the time of vacuum deposition, any one of an electron beam heating method, a resistance heating method, and an induction heating method is preferable. Moreover, in order to improve the adhesiveness with the base|substrate on which an inorganic vapor deposition layer is formed, and the compactness of an inorganic vapor deposition layer, you may employ|adopt a plasma assist method or an ion beam assist method for vapor deposition. Moreover, in order to improve the transparency of an inorganic vapor deposition layer, you may employ|adopt the reaction vapor deposition method which blows oxygen gas etc. at the time of vapor deposition to generate|occur|produce a reaction.

When the substrate (X) is layered, its thickness is preferably in the range of 1 to 1000 µm, more preferably in the range of 5 to 500 µm, from the viewpoint of improving the mechanical strength and workability of the obtained multilayered structure. Preferably, it is more preferable that it is in the range of 9-200 micrometers.

[Adhesive Layer (H)]

In the multilayer structure of the present invention, the layer (Y) and/or the layer (Z) may be laminated so as to be in direct contact with the substrate (X), but the substrate (X) and the layer (Y) and/or the layer (Z) The layer (Y) and/or the layer (Z) may be laminated|stacked on the base material (X) via the adhesive layer (H) disposed therebetween. According to this structure, the adhesiveness of the base material (X), the layer (Y), and/or the layer (Z) may be improved. The adhesive layer (H) may be formed of an adhesive resin. The adhesive layer (H) made of an adhesive resin can be formed by treating the surface of the substrate (X) with a known anchor coating agent or by applying a known adhesive to the surface of the substrate (X). As the adhesive, a two-component reactive polyurethane adhesive in which a polyisocyanate component and a polyol component are mixed and reacted is preferable. Moreover, by adding a small amount of additives, such as a well-known silane coupling agent, to an anchor coating agent and an adhesive agent, adhesiveness may be further improved. As a suitable example of a silane coupling agent, the silane coupling agent which has reactive groups, such as an isocyanate group, an epoxy group, an amino group, a ureide group, and a mercapto group, is mentioned. By strongly adhering the substrate (X) and the layer (Y) and/or the layer (Z) through the adhesive layer (H), gas barrier properties and The deterioration of the appearance can be more effectively suppressed.

By thickening the adhesive layer (H), the strength of the multilayer structure of the present invention can be increased. However, when the adhesive layer H is made too thick, the appearance tends to deteriorate. The thickness of the adhesive layer (H) is preferably in the range of 0.03 to 0.18 µm. According to this configuration, when processing such as printing or lamination is applied to the multilayer structure of the present invention, deterioration of gas barrier properties and appearance can be more effectively suppressed, and the packaging material using the multilayer structure of the present invention is dropped. strength can be increased. The thickness of the adhesive layer (H) is more preferably in the range of 0.04 to 0.14 µm, and still more preferably in the range of 0.05 to 0.10 µm.

[Configuration of multi-layered structure]

The multilayer structure (laminated body) of the present invention may be constituted only of the substrate (X), the layer (Y) and the layer (Z), and the substrate (X), the layer (Y), the layer (Z) and the adhesive layer (H) may be constituted only by The multilayer structure of the present invention may include a plurality of layers (Y) and/or a plurality of layers (Z). In addition, the multilayer structure of the present invention may include other members (for example, a thermoplastic resin film layer, a paper layer, an inorganic vapor deposition layer, etc.) other than the substrate (X), the layer (Y), the layer (Z) and the adhesive layer (H). layer, etc.) may be additionally included. The multilayer structure of the present invention having such other members (other layers, etc.) may be prepared, for example, after laminating the layers (Y) and (Z) directly on the substrate (X) or via the adhesive layer (H), followed by additional It can be manufactured by bonding or forming the said other member (another layer, etc.) directly or through an adhesive layer. By including such other members (such as another layer) in the multilayer structure, the properties of the multilayer structure can be improved or new properties can be imparted. For example, heat-sealing properties can be imparted to the multilayered structure of the present invention, and barrier properties and mechanical properties can be further improved.

In particular, when the outermost surface layer of the multilayer structure of the present invention is a polyolefin layer, heat sealing properties can be imparted to the multilayer structure or the mechanical properties of the multilayer structure can be improved. It is preferable that polyolefin is polypropylene or polyethylene from a viewpoint, such as an improvement of heat-sealing property and a mechanical characteristic. In addition, in order to improve the mechanical properties of the multilayer structure, as another layer, it is preferable to laminate at least one film selected from the group consisting of a film made of polyester, a film made of polyamide, and a film made of a hydroxyl group-containing polymer. do. From the viewpoint of improving the mechanical properties, the polyester is preferably polyethylene terephthalate (PET), the polyamide is preferably nylon-6, and the hydroxyl group-containing polymer is preferably an ethylene-vinyl alcohol copolymer. Moreover, you may provide the layer which consists of an anchor-coat layer and an adhesive agent between each layer as needed.

The multilayer structure of the present invention can be formed by laminating at least one set of layers (Y) and (Z) and at least one other layer (including a base material). Examples of other layers include a polyester layer, a polyamide layer, a polyolefin layer (a pigment-containing polyolefin layer, a heat-resistant polyolefin layer, or a biaxially stretched heat-resistant polyolefin layer may be sufficient), a hydroxyl group-containing polymer layer (for example, ethylene-vinyl alcohol copolymerization) body layer (hereinafter, may be abbreviated as "EVOH layer"), paper layer, inorganic vapor deposition film layer, thermoplastic elastomer layer, adhesive layer, and the like. As long as the multilayer structure comprises a substrate, a layer (Y) and a layer (Z), and at least one set of layers (Y) and (Z) are stacked adjacently, these other layers and layers (Y), layer ( There is no particular limitation on the number of Z) and the order of stacking. Further, as a preferred example, at least one set of the substrate (X), the layer (Y), and the layer (Z) is a multilayer having a structure in which the substrate (X)/layer (Y)/layer (Z) are laminated in this order. structures can be cited. In addition, these other layers can also be substituted by the molded object (molded object which has a three-dimensional shape) which consists of the material.

Specific examples of the configuration of the multilayer structure of the present invention are shown below. In addition, in the following specific examples, you may substitute each layer with the molded object (molded object which has a three-dimensional shape) which consists of the material. In addition, although the multilayer structure may have adhesive layers, such as a contact bonding layer (H), in the following specific example, description of the said contact bonding layer is abbreviate|omitted. In addition, in the following specification, the layer (YZ) means a structure in which the layer (Y) and the layer (Z) are laminated|stacked adjacently, and the order is layer (Y)/layer (Z) or layer (Z) Any of the /layers (Y) may be used.

(1) layer (YZ)/polyester layer,

(2) layer (YZ)/polyester layer/layer (YZ);

(3) layer (YZ)/polyamide layer,

(4) layer (YZ)/polyamide layer/layer (YZ);

(5) layer (YZ)/polyolefin layer;

(6) layer (YZ)/polyolefin layer/layer (YZ);

(7) layer (YZ)/hydroxyl group-containing polymer layer;

(8) layer (YZ)/hydroxyl group-containing polymer layer/layer (YZ);

(9) layer (YZ)/paper layer,

(10) layer (YZ)/paper layer/layer (YZ);

(11) layer (YZ)/inorganic vapor deposition layer/polyester layer;

(12) inorganic vapor deposition layer/layer (YZ)/polyester layer;

(13) layer (YZ)/inorganic vapor deposition layer/polyamide layer;

(14) inorganic vapor deposition layer/layer (YZ)/polyamide layer;

(15) layer (YZ)/inorganic vapor deposition layer/polyolefin layer;

(16) inorganic vapor deposition layer/layer (YZ)/polyolefin layer;

(17) layer (YZ)/inorganic vapor deposition layer/hydroxyl group-containing polymer layer;

(18) inorganic vapor deposition layer/layer (YZ)/hydroxyl group-containing polymer layer;

(19) layer (YZ)/polyester layer/polyamide layer/polyolefin layer;

(20) layer (YZ)/polyester layer/layer (YZ)/polyamide layer/polyolefin layer;

(21) polyester layer/layer (YZ)/polyamide layer/polyolefin layer;

(22) layer (YZ)/polyamide layer/polyester layer/polyolefin layer;

(23) layer (YZ)/polyamide layer/layer (YZ)/polyester layer/polyolefin layer;

(24) polyamide layer/layer (YZ)/polyester layer/polyolefin layer;

(25) layer (YZ)/polyolefin layer/polyamide layer/polyolefin layer;

(26) layer (YZ)/polyolefin layer/layer (YZ)/polyamide layer/polyolefin layer;

(27) polyolefin layer/layer (YZ)/polyamide layer/polyolefin layer;

(28) layer (YZ)/polyolefin layer/polyolefin layer;

(29) layer (YZ)/polyolefin layer/layer (YZ)/polyolefin layer;

(30) polyolefin layer/layer (YZ)/polyolefin layer;

(31) layer (YZ)/polyester layer/polyolefin layer;

(32) layer (YZ)/polyester layer/layer (YZ)/polyolefin layer;

(33) polyester layer/layer (YZ)/polyolefin layer;

(34) layer (YZ)/polyamide layer/polyolefin layer;

(35) layer (YZ)/polyamide layer/layer (YZ)/polyolefin layer;

(36) polyamide layer/layer (YZ)/polyolefin layer;

(37) layer (YZ)/polyester layer/paper layer;

(38) layer (YZ)/polyamide layer/paper layer;

(39) layer (YZ)/polyolefin layer/paper layer;

(40) polyolefin layer/paper layer/polyolefin layer/layer (YZ)/polyester layer/polyolefin layer;

(41) polyolefin layer/paper layer/polyolefin layer/layer (YZ)/polyamide layer/polyolefin layer;

(42) polyolefin layer/paper layer/polyolefin layer/layer (YZ)/polyolefin layer;

(43) paper layer/polyolefin layer/layer (YZ)/polyester layer/polyolefin layer;

(44) polyolefin layer/paper layer/layer (YZ)/polyolefin layer;

(45) paper layer/layer (YZ)/polyester layer/polyolefin layer;

(46) paper layer/layer (YZ)/polyolefin layer;

(47) layer (YZ)/paper layer/polyolefin layer;

(48) layer (YZ)/polyester layer/paper layer/polyolefin layer;

(49) polyolefin layer/paper layer/polyolefin layer/layer (YZ)/polyolefin layer/hydroxyl group-containing polymer layer;

(50) polyolefin layer/paper layer/polyolefin layer/layer (YZ)/polyolefin layer/polyamide layer;

(51) Polyolefin layer/paper layer/polyolefin layer/layer (YZ)/polyolefin layer/polyester layer.

According to the present invention, it is possible to obtain a multilayer structure satisfying one or both of the following performances. In a preferred example, the thickness of the layer (Y) (the sum of the thicknesses of each layer (Y) when the multilayer structure has two or more layers (Y)) is 2.0 µm or less (for example, 0.01 µm or more and 2.0 µm or less) ), satisfies the following performance. In addition, the detail of the measurement conditions of oxygen permeability is demonstrated in an Example.

(Performance 1) The oxygen permeability in the conditions of 20 degreeC and 85 %RH is 2 ml/(m<2>*day*atm) or less.

(Performance 2)

The oxygen permeability in the conditions of 20 degreeC and 85%RH after hold|maintaining for 5 minutes in the state extended by 5% on the conditions of 23 degreeC, 50%RH is 4 ml/(m<2>*day*atm) or less.

[purpose]

The multilayer structure of the present invention has excellent gas barrier properties, and can maintain gas barrier properties at a high level even when subjected to physical stress such as deformation or impact. In addition, according to the present invention, a multilayered structure excellent in appearance can be obtained. For this reason, the multilayer structure of this invention can be applied to various uses. For example, the product provided with the multilayer structure of the present invention may be a product including the multilayer structure as a packaging material or as a member of an electronic device that is a solar cell, display, or lighting device. A molded article may be sufficient as a packaging material, and it may have the shape of a bag. The member of the electronic device is, for example, a protective sheet that protects the surface of the electronic device body. In addition, the multilayer structure of the present invention may have a barrier property to water vapor in addition to the gas barrier property, and in that case, even when subjected to physical stress such as deformation or impact, the water vapor barrier property can be maintained at a high level. . In particular, when using for products, such as a solar cell member and a display member, this characteristic may contribute greatly to the durability of a product.

The multilayered structure of the present invention is particularly preferably used as a packaging material. Examples of uses other than packaging materials include display members such as LCD substrate films, organic EL substrate films, electronic paper substrate films, electronic device sealing films, PDP films, etc., LED films, IC tag films, solar Electronic device related members, such as solar cell members, such as a battery module, the back sheet for solar cells, and the protective film for solar cells; The member for optical communication, the flexible film for electronic devices, the diaphragm for fuel cells, the sealing film for fuel cells, the board|substrate film of various functional films, etc. are contained. When using as a display member, it is used as a low reflective film, for example.

This packaging material can be applied to a variety of uses, and is preferably used for applications in which barrier properties to oxygen are required, and applications in which the inside of the packaging material is substituted with various functional gases. For example, the packaging material of the present invention is preferably used as a packaging material for food. When used as a food packaging material, it is used especially suitably for the form which has fold lines, such as a stand-up pouch. In addition, the packaging material of the present invention may include, in addition to the packaging material for food, pharmaceuticals such as pesticides and pharmaceuticals; medical equipment; mechanical parts; industrial materials such as precision materials; It can be used suitably as a packaging material for packaging clothes etc.

In addition, the packaging material of the present invention can be used by processing into various molded articles. Such a molded article may be a molded container, a vertical umbilical cord filled seal bag, a vacuum packaging bag, a pouch such as a pouch with a spout, a laminate tube container, an infusion bag, a container lid material, a paper container, or a vacuum insulator. These packaging materials have a partition wall blocking the inside and the outside for maintaining water solubility, and this partition wall is provided with the multilayer structure of the present invention.

The molding container has a substrate previously molded into a predetermined shape, more specifically, to surround an interior (internal space) for accommodating contents, and a gas barrier film formed on the substrate, wherein the substrate and the gas barrier film constitute a partition wall. do. A molding container typically has shapes, such as a bottle and a tank. The substrate is usually molded to have an opening for introducing the contents into the interior space.

The vertical umbilical cord filling seal bag is a bag obtained by discharging a film material with a vertical umbilical cord filling machine (also referred to as a vertical umbilical cord filling packaging machine or the like). A vertical umbilical cord filling machine, for example, forms a bag with an open top by sealing (joining) the sides and the bottom while maintaining the side facing the supplied film material to be formed, and supplies the contents from above the bag. Fill it inside. Then, the vertical umbilical cord filling machine seals the upper part of the bag, cuts the upper part, and discharges it as a vertical umbilical cord filling seal bag. The longitudinal umbilical cord filling machine enables hygienic and efficient umbilicalization with less chance of human hand involvement. Various methods are applied to the umbilical cord filling by the vertical umbilical cord filling machine, but in either method, the contents are supplied from an opening at the upper side of the bag to the inside, and then the opening is sealed to produce a vertical umbilical cord filling seal bag. In the vertical umbilical cord filling seal bag, the film material has a multilayer structure and further constitutes a partition wall.

A vacuum packaging bag is a bag used in the state in which the inside of a bag was pressure-reduced. Since the inside of the bag is pressure-reduced, in a vacuum packaging bag, the film material blocking the inside of the bag and the outside of the bag is usually deformed so as to be in contact with the contents accommodated in the bag. The contents are typically foods such as whole corn, beans, sprouts, sprouts, chestnuts, tea leaves, meat, fish, and sweets. In the vacuum packaging bag, the film material is provided with a multilayer structure and further constitutes a partition wall.

A pouch is a container provided with a film material as a partition wall blocking the inside and the outside for accommodating the contents. Pouches are suitable for containing liquid or slurry contents, but can also be used for containing solid contents. The contents are typically beverages, seasonings, liquid other foods, and detergents, liquid soaps and other daily necessities. The pouch with spout has a main body formed using a film material, and a spout with a lid attached to the upper portion of the main body. There is also known a pouch with a chuck seal in which a chuck seal is provided on the periphery of the main body instead of a spout with a lid. A pouch provided with a bottom wall portion that imparts independence to the pouch is called a stand-up pouch (standing pouch). Gusseted pouches with gussets are also being manufactured. The flat pouch is manufactured by bonding film materials to each other at a seal part on the periphery. As for the flat pouch, the film material of 2 sheets may be joined by the periphery of every direction, and the three-way periphery may be sealed in the state which the film material of 1 sheet was folded|folded.

A laminated tube container is provided with a body part provided with a laminate film as a partition which blocks the inside and the outside of a container, and the pouring part for taking out the content accommodated in the inside of the container. The body part of the laminated tube container has, for example, a cylindrical shape with one end closed, and the pouring part is arrange|positioned at the other end side. In the laminate tube container, the laminate film material (film material) has a multilayer structure.

The infusion bag is a bag (sack) for accommodating infusions such as amino acid infusions, electrolyte infusions, carbohydrate infusions, and fat emulsions for infusions as contents. The infusion bag may include, in addition to the bag body for accommodating the contents, an inlet stopper member. In addition, the infusion bag may be provided with a hanging hole for hanging the bag. In the infusion bag, a film material blocking the inside and the outside for accommodating the infusion is provided with a multilayer structure.

The container lid material is provided with the film material which functions as a part of the partition which blocks the inside and the outside of a container in the state which combined with the container main body and formed the container. The container lid material is combined with the container body so as to seal the opening of the container body by a heat seal, bonding (seal) using an adhesive, or the like to form a container (a container with a lid) having a sealed space therein. The container lid material is usually joined to the container main body in the periphery. In this case, the central portion surrounded by the periphery faces the inner space of the container. A container main body is a molded object which has a cup shape, a tray shape, and another shape, for example, and is equipped with the flange part for sealing the lid material for containers, a wall surface part, etc.

A paper container is a container in which a partition wall blocking the inside and the outside for accommodating the contents includes a paper layer. A paper container has a shape, such as a gable top shape and a brick shape, for example. These shapes are equipped with the bottom wall part for becoming independent in a paper container.

A vacuum insulator is a heat insulating body in which the inside in which the core material was arrange|positioned was pressure-reduced provided with the covering material and the core material arrange|positioned inside surrounded by the covering material. As the core material, for example, a powder such as pearlite powder, a fiber material such as glass wool, a resin foam such as urethane foam, a hollow container, a honeycomb structure, or the like can be used. In a vacuum insulator, the covering material functioning as a partition is equipped with the multilayer structure.

Heat-sealing may be given to the said molded article (for example, a vertical umbilical cord filling sealing bag etc.). When heat sealing is implemented, it is necessary to arrange|position a heat-sealable layer in both the side used as the side used as the inner side of a molded article, or the side used as an outer side normally of a molded article. When the heat-sealable layer exists only on the side used as the inner side of a molded article (bag), the seal of a body part turns into a joint bonding seal normally. When the layer which can be heat-sealed exists in both the side used as the side used as the inner side of a molded article, and the side used as an outer side, the seal|sticker of a body part turns into a bag pasting seal normally. As a heat-sealable layer, a polyolefin layer (it may describe hereafter as "PO layer") is preferable.

The product including the multilayer structure of the present invention may be an electronic device provided with a protective sheet. This product is equipped with an electronic device main body and the protective sheet which protects the surface of the electronic device main body. This electronic device may be equipped with the electronic device main body, the sealing material for sealing the electronic device main body, and the protective sheet for protecting the surface of the electronic device main body. The encapsulant covers the entire surface of the electronic device main body 1 . In this case, a protective sheet is arrange|positioned via a sealing material on at least one surface of an electronic device main body. You may arrange|position a protective sheet through a sealing material also on the surface of the electronic device main body on the opposite side to this surface. Although the electronic device main body is not specifically limited, For example, Photoelectric conversion apparatuses, such as a solar cell, Information display apparatuses, such as an organic electroluminescent display, a liquid crystal display, electronic paper, Illumination apparatuses, such as an organic electroluminescent light emitting element. A sealing material is an arbitrary member added suitably according to the kind, use, etc. of an electronic device main body, EVA (ethylene-vinyl acetate resin), PVB (polyvinyl butyral), etc. are used.

Hereinafter, the multilayer film including the base material (X) and the layer (YZ) laminated on the base material (X) may be referred to as a barrier multilayer film. This barrier multilayer film is also one type of the multilayer structure of the present invention. The layer for providing various characteristics (for example, heat-sealing property) may be laminated|stacked on the barrier multilayer film. For example, the multilayer structure of the present invention may have the same structure as a barrier multilayer film/adhesive layer/polyolefin layer, or a polyolefin layer/adhesive layer/barrier multilayer film/adhesive layer/polyolefin layer. That is, the multilayered structure of the present invention may include a polyolefin layer disposed on one outermost surface. Moreover, the multilayer structure of this invention may contain the 1st polyolefin layer arrange|positioned at one outermost surface, and the 2nd polyolefin layer arrange|positioned at the other outermost surface. The first polyolefin layer and the second polyolefin layer may be the same or different.

The vertical cord filling seal bag may be formed by laminating at least one barrier multilayer film and at least one other layer. Examples of the other layer include a polyester layer, a polyamide layer, a polyolefin layer, a paper layer, an inorganic vapor deposition film layer, an EVOH layer, an adhesive layer, and the like. Although there is no restriction|limiting in particular in the number and lamination|stacking order of these layers, When heat-sealing is implemented, the structure for this is employ|adopted.

As a structure of a multilayer structure especially preferable as a vertical cord filling sealing bag, the structure of barrier multilayer film/polyamide layer/PO layer, barrier multilayer film/PO layer, PO layer/barrier multilayer film/PO layer is mentioned. In these structures, for example, a polyamide film can be used as the substrate of the barrier multilayer film. The vertical umbilical cord filling seal bag maintains its gas barrier properties even when subjected to physical stress such as deformation or impact. An adhesive layer may be provided between the layers of each layer constituting the vertical umbilical cord filling seal bag and the layers. In addition, when the layer (YZ) of the multilayered structure of the present invention is on one side of the substrate, the layer (YZ) may face either the outside or the inside of the vertical umbilical cord filling seal bag.

The molded article including the multilayer structure of the present invention may be a vacuum packaging bag for packaging food or the like containing solid content. The vacuum packaging bag is excellent in gas barrier properties, and even when subjected to physical stress such as deformation or impact, the gas barrier properties are maintained. For this purpose, the vacuum packaging bag hardly deteriorates the gas barrier properties over a long period of time. Since the vacuum packaging bag is flexible and easily adheres to foods containing solid content, degassing during vacuum packaging is easy. For this reason, the said vacuum packaging bag can reduce residual oxygen in a vacuum packaging body, and is excellent in the long-term storage property of a food. Moreover, since it is hard to generate|occur|produce a angular|angular, bent, or a part after vacuum packaging, it is hard to generate|occur|produce defects, such as a pinhole and a crack. Moreover, according to the said vacuum packaging bag, generation|occurrence|production of a pinhole by friction between vacuum packaging bags or a vacuum packaging bag and a corrugated cardboard can be suppressed. In addition, the vacuum packaging bag has excellent gas barrier properties, and since the gas barrier properties are maintained even when subjected to physical stress such as deformation or impact, deterioration of the quality of the contents (eg, food) can be suppressed over a long period of time. can

The vacuum packaging bag may be formed by laminating at least one barrier multilayer film and at least one other layer. Examples of the other layer include a polyester layer, a polyamide layer, a polyolefin layer, an inorganic vapor deposition film layer, an EVOH layer, an adhesive layer, and the like. Although there is no restriction|limiting in particular in the number and lamination|stacking order of these layers, When heat-sealing is implemented, the structure for this is employ|adopted.

As a structure of a multilayered structure particularly preferable as a vacuum packaging bag, a structure such as a barrier multilayer film/polyamide layer/PO layer and a polyamide layer/barrier multilayer film/PO layer is exemplified. In these structures, for example, a polyamide film can be used as the substrate of the barrier multilayer film. A vacuum packaging bag using such a multilayer structure is particularly excellent in gas barrier properties after vacuum packaging and after vacuum packaging and heat sterilization. An adhesive layer may be provided between the layers of the respective layers. In addition, when the layer (YZ) is laminated|stacked only on one side of a base material, the layer (YZ) may be outside or inside a vacuum packaging bag with respect to a base material.

The molded article including the multilayer structure of the present invention may be a pouch with a spout for packaging various liquid substances. The said pouch with spout can be used as a container, such as a liquid drink (for example, soft drink), a jelly drink, yogurt, a fruit sauce, a seasoning, functional water, and a liquid food. The pouch with spout can also be suitably used as a container for liquid pharmaceuticals, such as amino acid infusions, electrolyte infusions, carbohydrate infusions, and fat emulsions for infusions. The pouch with spout has excellent gas barrier properties, and the gas barrier properties are maintained even when subjected to physical stress such as deformation or impact. For this reason, by using the said pouch with spout, it is possible to prevent deterioration of the contents even after transportation and long-term storage. In addition, since the pouch with spout can maintain good transparency, it is easy to check the contents or to check the quality of the contents due to deterioration.

The pouch with spout may be formed by laminating at least one barrier multilayer film and at least one other layer. Examples of the other layer include a polyester layer, a polyamide layer, a polyolefin layer, an inorganic vapor deposition film layer, an EVOH layer, an adhesive layer, and the like. Although there is no restriction|limiting in particular in the number and lamination|stacking order of these layers, When heat-sealing is implemented, the structure for this is employ|adopted.

As a structure of a multilayer structure especially preferable as a pouch with spout, the structure of barrier multilayer film/polyamide layer/PO layer, and polyamide layer/barrier multilayer film/PO layer is mentioned. An adhesive layer may be provided between the layers of the respective layers. In addition, when the layer (YZ) is laminated|stacked only on one side of a base material, the layer (YZ) may be outside or inside a pouch with a spout with respect to a base material.

The molded article including the multilayer structure of the present invention may be a laminate tube container for packaging cosmetics, pharmaceuticals, pharmaceuticals, food, toothpaste, and the like. The laminate tube container is excellent in gas barrier properties, and the gas barrier properties are maintained even when subjected to physical stress such as deformation or impact. In addition, since the laminate tube container has good transparency, it is easy to confirm the contents or to confirm the quality of the contents due to deterioration.

The laminate tube container may be formed by laminating at least one barrier multilayer film and at least one other layer. Examples of the other layer include a polyamide layer, a polyolefin layer (which may be a pigment-containing polyolefin layer), an inorganic vapor deposition film layer, an EVOH layer, an adhesive layer, and the like. Although there is no restriction|limiting in particular in the number and lamination|stacking order of these layers, When heat-sealing is implemented, the structure for this is employ|adopted.

A particularly preferable configuration for the laminate tube container includes a configuration of PO layer/barrier multilayer film/PO layer, and PO layer/pigment-containing PO layer/PO layer/barrier multilayer film/PO layer. You may arrange|position an adhesive layer between the layers of said each layer. Further, when the layer (YZ) is laminated on only one side of the substrate, the layer (YZ) may be outside or inside the laminate tube container with respect to the substrate.

The molded article including the multilayer structure of the present invention may be an infusion bag, for example, an infusion bag filled with a liquid medicine such as an amino acid infusion, an electrolyte infusion, a carbohydrate infusion, and a fat emulsion for infusion. The infusion bag is excellent in gas barrier properties, and the gas barrier properties are maintained even when subjected to physical stress such as deformation or impact. For this reason, according to the said infusion bag, even before heat sterilization, during heat sterilization, after heat sterilization, after transportation, and after storage, it is possible to prevent deterioration of the filled liquid medicine.

The infusion bag may be formed by laminating at least one barrier multilayer film and at least one other layer. Examples of the other layer include a polyamide layer, a polyolefin layer, an inorganic vapor deposition film layer, an EVOH layer, a thermoplastic elastomer layer, an adhesive layer, and the like. Although there is no restriction|limiting in particular in the number and lamination|stacking order of these layers, When heat-sealing is implemented, the structure for this is employ|adopted.

As a structure of a multilayer structure especially preferable as an infusion bag, the structure of a barrier multilayer film/polyamide layer/PO layer, and a polyamide layer/barrier multilayer film/PO layer is mentioned. You may arrange|position an adhesive layer between the layers of said each layer. In addition, when the layer (YZ) is laminated on only one surface of the substrate, the layer (YZ) may be outside or inside the infusion bag with respect to the substrate.

The molded article including the multilayered structure of the present invention may be a lid material for a container filled with foods such as processed livestock meat, processed vegetables, processed seafood, and fruits. The container lid material is excellent in gas barrier properties, and since the gas barrier properties are maintained even when subjected to physical stress such as deformation or impact, deterioration of the quality of the food as a content can be suppressed over a long period of time. And the said container lid material is used suitably as a container lid material used for preservation|save of contents, such as foodstuff.

The container lid material may be formed by laminating at least one barrier multilayer film and at least one other layer. Examples of the other layer include a polyamide layer, a polyolefin layer, an inorganic vapor deposition film layer, an EVOH layer, a polyester layer, a paper layer, an adhesive layer, and the like. Although there is no restriction|limiting in particular in the number and lamination|stacking order of these layers, When heat-sealing is implemented, the structure for this is employ|adopted.

As a structure of a multilayer structure especially preferable as a lid material for containers, the structure of a barrier multilayer film/polyamide layer/PO layer, and a barrier multilayer film/PO layer is mentioned. In these structures, for example, a polyamide film can be used as the substrate of the barrier multilayer film. You may provide a contact bonding layer between the layers of each said layer. In addition, when the layer (YZ) of the multilayer structure exists on one side of a base material, the layer (YZ) may be inside rather than a base material (container side), and may exist outside a base material.

The molded article including the multilayer structure of the present invention may be a paper container. Even if the said paper container gives a bending process, there is little fall of gas-barrier property. Moreover, since the said paper container has favorable transparency of the layer (YZ), it is used suitably for a container with a window. Moreover, the said paper container is suitable also for heating by a microwave oven.

The paper container may be formed by laminating at least one barrier multilayer film and at least one other layer. Examples of other layers include a polyester layer, a polyamide layer, a polyolefin layer (which may be a heat-resistant polyolefin layer or a biaxially stretched heat-resistant polyolefin layer), an inorganic vapor deposition film layer, a hydroxyl group-containing polymer layer, a paper layer, and an adhesive layer. . Although there is no restriction|limiting in particular in the number and lamination|stacking order of these layers, When heat-sealing is implemented, the structure for this is employ|adopted.

As a structure of a multilayer structure especially preferable as a paper container, the structure of heat-resistant polyolefin layer/paper layer/heat-resistant polyolefin layer/barrier-resistant multilayer film/heat-resistant polyolefin layer is mentioned. You may arrange|position an adhesive layer between the layers of said each layer. In the above example, the heat-resistant polyolefin layer is composed of, for example, either a biaxially stretched heat-resistant polyolefin film or an unstretched heat-resistant polyolefin film. From the viewpoint of easiness of molding, the heat-resistant polyolefin layer disposed on the outermost layer of the multilayer structure is preferably an unstretched polypropylene film. Similarly, it is preferable that the heat-resistant polyolefin layer disposed on the inner side of the outermost layer of the multilayer structure is an unstretched polypropylene film. In a preferred example, all of the heat-resistant polyolefin layers constituting the multilayer structure are unstretched polypropylene films.

The molded article including the multilayered structure of the present invention may be a vacuum insulator that can be used for various applications requiring cold storage or thermal insulation. Since the vacuum insulator can maintain its thermal insulation effect over a long period of time, it is used as an insulator for household appliances such as refrigerators, hot water supply facilities and rice cookers, as well as for residential insulation used for walls, ceilings, roof backsides and floors, vehicle roofing materials, It can be used for heat insulation panels, such as a vending machine.

The vacuum insulator may be formed by laminating at least one barrier multilayer film and at least one other layer. Examples of the other layer include a polyester layer, a polyamide layer, a polyolefin layer, an adhesive layer, and the like. Although there is no restriction|limiting in particular in the number and lamination|stacking order of these layers, When heat-sealing is implemented, the structure for this is employ|adopted.

As a structure of a multilayer structure especially preferable as a vacuum insulator, the structure of a barrier multilayer film/polyamide layer/PO layer, and a polyamide layer/barrier multilayer film/PO layer is mentioned. You may provide a contact bonding layer between the layers of each said layer. In addition, when the layer (YZ) is laminated|stacked only on one surface of a base material, the layer (YZ) may be outside or inside a vacuum insulator with respect to a base material.

[Method for manufacturing multi-layered structure]

Hereinafter, the manufacturing method of the multilayer structure of this invention is demonstrated. According to this method, the multilayered structure of the present invention can be easily manufactured. Since the materials used in the method for manufacturing the multilayer structure of the present invention and the structure of the multilayer structure are the same as those described above, the description of overlapping parts may be omitted in some cases. Description of the multilayered structure of the present invention for, for example, the substrate (X), the layer (Y), the layer (Z), the metal oxide (A), the phosphorus compound (B), the polymer (C), and the polymer (E) It is possible to apply the description in In addition, the matters described with respect to this manufacturing method are applicable to the multilayer structure of the present invention. In addition, the matters described for the multilayer structure of the present invention can be applied to the manufacturing method of the present invention.

The manufacturing method of this invention is a manufacturing method of the multilayer structure which has each one or more layers of a base material (X), a layer (Y), and a layer (Z). Layer (Y) contains aluminum atoms. The layer (Z) contains a polymer (E) having a plurality of phosphorus atoms. At least one set of layers (Y) and (Z) are laminated adjacently. The manufacturing method of this invention includes the process (IV) of forming a layer (Z) by apply|coating the coating liquid (V) containing the polymer (E) which has a plurality of phosphorus atoms.

In addition, when the layer (Y) of the multilayer structure of the present invention is a layer (YB) that is a deposited layer of aluminum or a layer (YC) that is a deposited layer of aluminum oxide, the layer (YB) and the layer (YC) are the above Since it can be formed by one general vapor deposition method, a detailed description thereof is omitted. In the following, when the layer (Y) included in the multilayer structure of the present invention is a layer (YA) containing a reaction product (R) formed by reacting at least a metal oxide (A) containing aluminum and a phosphorus compound (B) will be described in particular detail. In addition, regarding the formation method of the layer Z (process (IV) mentioned later), the same formation method is employ|adopted in any case where the layer Y is the layer YA, the layer YB, and the layer YC. can do.

When the layer (Y) included in the multilayer structure of the present invention is a layer (YA) containing at least a reaction product (R) formed by reacting a metal oxide (A) containing aluminum and a phosphorus compound (B), the present invention The manufacturing method of the multilayer structure of includes steps (I), (II), (III) and (IV). In step (I), by mixing the metal oxide (A) containing at least aluminum, the at least 1 sort(s) of compound containing the site|part which can react with the metal oxide (A), and a solvent, a metal oxide (A), the said at least A coating solution (U) containing one compound and the solvent is prepared. In process (II), the precursor layer of the layer (YA) is formed on the base material (X) by apply|coating the coating liquid (U) on the base material (X). In a process (III), the layer (YA) is formed on the base material (X) by heat-processing the precursor layer at the temperature of 110 degreeC or more. And in the process (IV), the layer (Z) is formed by apply|coating the coating liquid (V) containing the polymer (E) which has two or more phosphorus atoms. In addition, although the said process is typically performed in order of (I), (II), (III), and (IV), when the layer (Z) is formed between the base material (X) and the layer (YA), , the step (IV) may be performed before the step (II). Moreover, it is also possible to implement process (III) after process (IV) so that it may mention later.

[Process (I)]

At least one compound containing a site capable of reacting with the metal oxide (A) used in the step (I) is hereinafter sometimes referred to as “at least one compound (Z)”. In step (I), the metal oxide (A), at least 1 sort(s) of compound (Z), and a solvent are mixed at least. From one viewpoint, in the process (I), a metal oxide (A) and the raw material containing at least 1 sort(s) of compound (Z) are made to react in a solvent. The raw material may contain other compounds in addition to the metal oxide (A) and at least one compound (Z). Typically, the metal oxide (A) is mixed in the form of particles.

In the coating liquid (U), the number of moles of phosphorus atoms to be contained in the number of moles (N _M) and the compound (B) of the metal atom (M) constituting the metal oxide (A) (N _P) is, 1.0≤ (number of moles (N _M ))/(Number of moles (N _P )) ≤ 3.6. Since the preferable range of the value of (number of moles (N _M ))/(number of moles (N _P )) was mentioned above, the overlapping description is abbreviate|omitted.

At least 1 type of compound (Z) contains a phosphorus compound (B). It is preferable that the number of moles of the metal atoms contained in the at least one compound (Z) is in the range of 0 to 1 times the number of moles of the phosphorus atoms contained in the phosphorus compound (B). Typically, the at least one compound (Z) is a compound containing a plurality of sites capable of reacting with the metal oxide (A), and the number of moles of metal atoms contained in the at least one compound (Z) is a compound ( It exists in the range of 0 to 1 times the number of moles of phosphorus atoms contained in B).

The ratio of (the number of moles of metal atoms contained in at least one compound (Z))/(the number of moles of phosphorus atoms contained in the phosphorus compound (B)) is in the range of 0 to 1 (eg, in the range of 0 to 0.9) By doing so, a multilayer structure having more excellent gas barrier properties is obtained. This ratio is preferably 0.3 or less, more preferably 0.05 or less, still more preferably 0.01 or less, and may be 0 in order to further improve the gas barrier properties of the multilayered structure. Typically, at least 1 type of compound (Z) consists only of a phosphorus compound (B). In step (I), the said ratio can be reduced easily.

The step (I) preferably includes the following steps (a) to (c).

Step (a): A step of preparing the liquid (S) containing the metal oxide (A).

Process (b): The process of preparing the solution (T) containing a phosphorus compound (B).

Step (c): A step of mixing the liquid (S) and the solution (T) obtained in the steps (a) and (b).

A process (b) may be implemented before a process (a), may be implemented simultaneously with a process (a), and may be implemented after a process (a). Hereinafter, each process is demonstrated more concretely.

In the step (a), the liquid (S) containing the metal oxide (A) is prepared. The liquid S is a solution or a dispersion liquid. The said liquid (S) can be prepared by the method employ|adopted by the well-known sol-gel method, for example. For example, the compound (L)-based component described above, water, and, if necessary, an acid catalyst or an organic solvent are mixed, and the compound (L)-based component is condensed or hydrolyzed by a method employed in a known sol-gel method. It can be prepared by condensing. The dispersion liquid of the metal oxide (A) obtained by condensing or hydrolytically condensing the compound (L)-based component can be used as it is as the liquid (S) containing the metal oxide (A). However, if necessary, the dispersion may be subjected to a specific treatment (eg, peptization as described above, addition or reduction of a solvent for concentration control, etc.).

The step (a) may include a step of condensing (for example, hydrolysis condensation) at least one selected from the group consisting of compound (L) and a hydrolyzate of compound (L). Specifically, in the step (a), the compound (L), the partial hydrolyzate of the compound (L), the complete hydrolyzate of the compound (L), the partial hydrolysis-condensation product of the compound (L), and the compound (L) You may also include the process of condensing or hydrolyzing-condensing at least 1 sort(s) selected from the group which consists of a part of complete hydrolyzate condensed.

Moreover, as another example of the method for preparing the liquid S, the method including the following processes is mentioned. First, a metal is vaporized as a metal atom by thermal energy, and the metal atom is brought into contact with a reactive gas (oxygen) to generate molecules and clusters of a metal oxide. Then, the particle|grains of a metal oxide (A) with a small particle diameter are manufactured by cooling these in an instant. Next, by dispersing the particles in water or an organic solvent, a liquid (S) (a dispersion containing a metal oxide (A)) is obtained. In order to improve the dispersibility to water or an organic solvent, you may surface-treat with respect to the particle|grains of a metal oxide (A), or you may add stabilizers, such as surfactant. Moreover, you may improve the dispersibility of a metal oxide (A) by controlling pH.

As another example of the method for preparing the liquid (S), the bulk metal oxide (A) is pulverized using a pulverizer such as a ball mill or a jet mill, and the liquid (S) ( Dispersion liquid containing a metal oxide (A)) is mentioned. However, in this case, it may become difficult to control the shape and size distribution of the particle|grains of a metal oxide (A).

There is no restriction|limiting in particular in the kind of organic solvent which can be used in a process (a), For example, alcohols, such as methanol, ethanol, isopropanol, and normal propanol, are used suitably.

The content rate of the metal oxide (A) in the liquid (S) is preferably in the range of 0.1 to 40 mass%, more preferably in the range of 1 to 30 mass%, and in the range of 2 to 20 mass% more preferably.

In a process (b), the solution (T) containing a phosphorus compound (B) is prepared. The solution (T) can be prepared by dissolving the phosphorus compound (B) in a solvent. When the solubility of a phosphorus compound (B) is low, you may accelerate|stimulate melt|dissolution by heat processing or ultrasonic processing.

Although what is necessary is just to select suitably the solvent used for preparation of the solution (T) according to the kind of phosphorus compound (B), it is preferable to contain water. As long as it does not interfere with the dissolution of the phosphorus compound (B), the solvent may include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran, dioxane, trioxane, and dimethoxyethane; ketones such as acetone and methyl ethyl ketone; glycols such as ethylene glycol and propylene glycol; glycol derivatives such as methyl cellosolve, ethyl cellosolve, and n-butyl cellosolve; glycerin; acetonitrile; amides such as dimethylformamide; dimethyl sulfoxide; You may contain sulfolane etc.

It is preferable that the content rate of the phosphorus compound (B) in the solution (T) exists in the range of 0.1-99 mass %, It is more preferable to exist in the range of 0.1-95 mass %, It is in the range of 0.1-90 mass % more preferably. In addition, the content rate of the phosphorus compound (B) in the solution (T) may be in the range of 0.1-50 mass %, may be in the range of 1-40 mass %, and may exist in the range of 2-30 mass %. .

In the step (c), the liquid (S) and the solution (T) are mixed. When mixing the liquid (S) and the solution (T), in order to suppress a local reaction, it is preferable to mix while suppressing the addition rate and performing strong stirring. At this time, the solution T may be added to the stirring liquid S, or the liquid S may be added to the stirring solution T. When mixing in the step (c), the temperature of the liquid (S) and the temperature of the solution (T) are all preferably 50°C or lower, more preferably all 30°C or lower, and still more preferably all 20°C or lower. . By setting these temperatures at the time of mixing to 50°C or less, the metal oxide (A) and the phosphorus compound (B) are uniformly mixed, and the gas barrier properties of the resulting multilayered structure can be improved. Moreover, by continuing stirring for about 30 minutes further from the time of completion of mixing, the coating liquid (U) excellent in storage stability may be obtained.

In addition, the coating liquid (U) may contain a polymer (C). The method in particular of making the coating liquid (U) contain the polymer (C) is not restrict|limited. For example, after adding the polymer (C) in the form of powder or pellets to the liquid (S), the solution (T), or the mixed solution of the liquid (S) and the solution (T), it may be dissolved. Moreover, you may add and mix the solution of the polymer (C) to the liquid (S), the solution (T), or the mixed liquid of the liquid (S) and the solution (T). Moreover, you may add and mix the liquid (S), the solution (T), or the liquid mixture of the liquid (S) and the solution (T) to the solution of the polymer (C). When mixing the liquid (S) and the solution (T) in the step (c) by containing the polymer (C) in either the liquid (S) or the solution (T) before the step (c), the metal oxide ( The reaction rate between A) and the phosphorus compound (B) is moderated, and as a result, a coating liquid (U) excellent in stability with time may be obtained.

When the coating liquid (U) contains the polymer (C), the multilayer structure including the layer (YA) containing the polymer (C) can be easily produced.

The coating liquid (U) may contain at least one acid compound (D) selected from acetic acid, hydrochloric acid, nitric acid, trifluoroacetic acid, and trichloroacetic acid as needed. Below, the said at least 1 sort(s) of acid compound (D) may be abbreviated simply as "acid compound (D)." The method in particular of making the coating liquid (U) contain the acid compound (D) is not restrict|limited. For example, the acid compound (D) may be added as it is and mixed with the liquid (S), the solution (T), or the mixed liquid of the liquid (S) and the solution (T). Moreover, you may add and mix the solution of the acid compound (D) to the liquid (S), the solution (T), or the mixed liquid of the liquid (S) and the solution (T). Moreover, you may add and mix the liquid (S), the solution (T), or the liquid mixture of the liquid (S) and the solution (T) to the solution of the acid compound (D). When either the liquid (S) or the solution (T) contains the acid compound (D) before the step (c), when the liquid (S) and the solution (T) are mixed in the step (c), the metal oxide The reaction rate between (A) and the phosphorus compound (B) is moderated, and as a result, a coating liquid (U) excellent in temporal stability may be obtained.

In the coating liquid (U) containing the acid compound (D), the reaction between the metal oxide (A) and the phosphorus compound (B) is suppressed, and precipitation and aggregation of the reactants in the coating liquid (U) can be suppressed. For this reason, by using the coating liquid (U) containing the acid compound (D), the appearance of the obtained multilayered structure may be improved. In addition, since the boiling point of the acid compound (D) is 200° C. or less, the acid compound (D) can be easily removed from the layer (YA) by volatilizing the acid compound (D) in the manufacturing process of the multilayer structure. can

It is preferable to exist in the range of 0.1-5.0 mass %, and, as for the content rate of the acid compound (D) in the coating liquid (U), it is more preferable to exist in the range of 0.5-2.0 mass %. In these ranges, the effect by addition of the acid compound (D) is obtained, and the removal of the acid compound (D) is easy. When the acid component remains in the liquid (S), the amount of the acid compound (D) to be added may be determined in consideration of the residual amount.

The liquid obtained by mixing in the step (c) can be used as it is as the coating liquid (U). In this case, the solvent contained in the liquid (S) or the solution (T) becomes the solvent of the coating liquid (U). Further, the coating liquid (U) may be prepared by treating the liquid obtained by mixing in the step (c). For example, you may perform processes, such as addition of an organic solvent, adjustment of pH, adjustment of a viscosity, and addition of an additive.

An organic solvent may be added to the liquid obtained by mixing in the step (c) within a range in which stability of the obtained coating liquid (U) is not impaired. By addition of the organic solvent, application|coating of the coating liquid (U) to the base material (X) in process (II) may become easy. As an organic solvent, it is preferable to mix uniformly in the coating liquid (U) obtained. As an example of a preferable organic solvent, For example, Alcohol, such as methanol, ethanol, n-propyl, isopropanol; ethers such as tetrahydrofuran, dioxane, trioxane, and dimethoxyethane; ketones such as acetone, methyl ethyl ketone, methyl vinyl ketone, and methyl isopropyl ketone; glycols such as ethylene glycol and propylene glycol; glycol derivatives such as methyl cellosolve, ethyl cellosolve, and n-butyl cellosolve; glycerin; acetonitrile; amides such as dimethylformamide and dimethylacetamide; dimethyl sulfoxide; Sulfolane etc. are mentioned.

From the viewpoint of storage stability of the coating liquid (U) and the applicability of the coating liquid (U) to the substrate, the solid content concentration of the coating liquid (U) is preferably in the range of 1 to 20 mass%, and 2 to 15 mass% It is more preferable to exist in the range, and it is still more preferable to exist in the range of 3-10 mass %. The solid content concentration of the coating liquid (U) is determined by, for example, adding a predetermined amount of the coating liquid (U) to a container, removing volatiles such as solvents at a temperature of 100 ° C for each container, and determining the mass of the remaining solid content first It can be calculated by dividing by the mass of the coating solution (U) added to . At that time, the mass of the remaining solid content is measured every time it is dried for a certain period of time, and the mass when the mass difference of two consecutive times reaches a level that can be ignored is taken as the mass of the remaining solid content, and the solid content concentration is calculated. desirable.

From the viewpoint of storage stability of the coating solution (U) and the gas barrier properties of the multilayer structure, the pH of the coating solution (U) is preferably in the range of 0.1 to 6.0, more preferably in the range of 0.2 to 5.0, and more preferably in the range of 0.5 to 4.0 It is more preferable to be in the range of

The pH of the coating liquid (U) can be adjusted by a known method, for example, by adding an acidic compound or a basic compound. Examples of the acidic compound include hydrochloric acid, nitric acid, sulfuric acid, acetic acid, butyric acid, and ammonium sulfate. Examples of the basic compound include sodium hydroxide, potassium hydroxide, ammonia, trimethylamine, pyridine, sodium carbonate, and sodium acetate.

The coating liquid (U) tends to change state with the lapse of time, and finally becomes a gel-like composition or causes precipitation. The time until such a state change depends on the composition of the coating liquid U. In order to apply the coating liquid U on the base material X stably, it is preferable that the viscosity of the coating liquid U is stable over a long period of time. The solution (U) has a viscosity measured with a Brookfield viscometer (Type B viscometer: 60 rpm) within 5 times of the reference viscosity even after standing at 25° C. for 2 days with the viscosity at the completion of step (I) as the reference viscosity. It is preferable to prepare it so that When the viscosity of the coating liquid (U) is in the above range, a multilayer structure having excellent storage stability and better gas barrier properties is often obtained.

As a method of adjusting the viscosity of the coating liquid (U) so that it is within the above range, for example, a method such as adjusting the concentration of solid content, adjusting pH, or adding a viscosity adjusting agent can be adopted. Examples of the viscosity modifier include carboxymethyl cellulose, starch, bentonite, gum tragacanth, stearate, alginate, methanol, ethanol, n-propanol, and isopropanol.

As long as the effect of the present invention is obtained, the coating liquid (U) may contain substances other than the substances described above. For example, the coating liquid U may include inorganic metal salts such as carbonate, hydrochloride, nitrate, hydrogencarbonate, sulfate, hydrogensulfate, borate, and aluminate; organic acid metal salts such as oxalate, acetate, tartrate and stearate; metal complexes of acetylacetonate metal complexes (such as aluminum acetylacetonate), cyclopentadienyl metal complexes (such as titanocene), and cyano metal complexes; layered clay compounds; crosslinking agent; high molecular compounds other than the polymer (C); plasticizer; antioxidants; UV absorbers; You may contain a flame retardant etc.

[Process (II)]

In process (II), the precursor layer of the layer (YA) is formed on the base material (X) by apply|coating the coating liquid (U) on the base material (X). The coating liquid (U) may be directly applied on at least one surface of the substrate (X). In addition, before applying the coating liquid (U), the surface of the substrate (X) is treated with a known anchor coating agent, or a known adhesive is applied to the surface of the substrate (X), etc. An adhesive layer (H) may be formed. In addition, the precursor layer of the layer (YA) may be formed on the layer (Z) by applying the coating solution (U) on the layer (Z) previously formed on the substrate (X) by the step (IV) described later.

Further, the coating liquid U may be subjected to degassing and/or degassing treatment as necessary. As a method of the degassing and/or degassing treatment, there are, for example, methods by evacuation, heating, centrifugation, ultrasonic waves, or the like, but a method including evacuation can be preferably used.

The viscosity measured by a Brookfield rotational viscometer (SB type viscometer: rotor No. 3, rotational speed 60 rpm) as the viscosity of the coating liquid (U) when applied in step (II) is 3000 mPa·s at the temperature at the time of application It is preferable that it is less than or equal to, and it is more preferable that it is 2000 mPa*s or less. When the viscosity is 3000 mPa·s or less, the leveling property of the coating liquid (U) is improved, and a multilayered structure having more excellent external appearance can be obtained. The viscosity of the coating liquid (U) when applied in the step (II) can be adjusted by the concentration, temperature, stirring time after mixing in step (c), and stirring intensity. For example, by performing stirring after mixing of a process (c) for a long time, a viscosity may be made low.

A method of applying the coating liquid (U) on the substrate (X) is not particularly limited, and a known method can be employed. Preferred methods include, for example, a casting method, a dipping method, a roll coating method, a gravure coating method, a screen printing method, a reverse coating method, a spray coating method, a kiss coating method, a die coating method, a metalling bar coating method, and a chamber doctor combination. A coat method, a curtain coat method, a bar coat method, etc. are mentioned.

Usually, in the process (II), the precursor layer of the layer (YA) is formed by removing the solvent in the coating liquid (U). There is no restriction|limiting in particular in the method of removing a solvent, A well-known drying method can be applied. Specifically, drying methods, such as a hot air drying method, a hot roll contact method, an infrared heating method, and a microwave heating method, can be applied individually or in combination. It is preferable that a drying temperature is 0-15 degreeC or more lower than the flow initiation temperature of the base material (X). When the coating liquid (U) contains the polymer (C), the drying temperature is preferably 15 to 20°C or more lower than the thermal decomposition start temperature of the polymer (C). The drying temperature is preferably in the range of 70 to 200°C, more preferably in the range of 80 to 180°C, still more preferably in the range of 90 to 160°C. Removal of the solvent may be performed under normal pressure or under reduced pressure. In addition, you may remove a solvent by the heat processing in process (III) mentioned later.

In the case of laminating the layer (YA) on both sides of the layered substrate (X), the coating solution (U) is applied to one side of the substrate (X), and then the solvent is removed to form the first layer (the first layer (YA) The second layer (precursor layer of the second layer YA) may be formed by forming the precursor layer) and then applying the coating solution U to the other surface of the substrate X, and then removing the solvent. The composition of the coating liquid U applied to each surface may be the same or different.

When laminating the layer YA on a plurality of surfaces of the substrate X having a three-dimensional shape, a layer (precursor layer of the layer YA) may be formed for each surface by the above method. Alternatively, a plurality of layers (precursor layers of the layer YA) may be simultaneously formed by applying the coating liquid U to a plurality of surfaces of the substrate X at the same time and drying it.

[Process (III)]

In the step (III), the layer (YA) is formed by heat-treating the precursor layer (the precursor layer of the layer (YA)) formed in the step (II) at a temperature of 110°C or higher.

In the step (III), a reaction in which particles of the metal oxide (A) are bonded through a phosphorus atom (a phosphorus atom derived from the phosphorus compound (B)) proceeds. From another point of view, in step (III), a reaction in which a reaction product (R) is produced proceeds. In order to sufficiently advance the reaction, the heat treatment temperature is 110°C or higher, preferably 120°C or higher, more preferably 140°C or higher, more preferably 170°C or higher, and still more preferably 190°C or higher. When the heat treatment temperature is low, the time required to obtain a sufficient reactivity becomes long, which causes a decrease in productivity. A preferable upper limit of the heat treatment temperature varies depending on the type of the substrate (X) or the like. For example, when using the thermoplastic resin film which consists of a polyamide-type resin as base material (X), it is preferable that the temperature of heat processing is 190 degrees C or less. Moreover, when using the thermoplastic resin film which consists of a polyester resin as base material (X), it is preferable that the temperature of heat processing is 220 degrees C or less. The heat treatment can be performed in air, in a nitrogen atmosphere, or in an argon atmosphere.

The time of the heat treatment is preferably in the range of 0.1 second to 1 hour, more preferably in the range of 1 second to 15 minutes, and still more preferably in the range of 5 to 300 seconds. An example of the heat treatment is performed in a range of 110 to 220°C (eg, in a range of 140 to 220°C) for 0.1 second to 1 hour. In addition, in the heat treatment of another example, in the range of 170-200 degreeC, it is implemented for 5-300 second (for example, 10-300 second).

The method of the present invention for producing a multilayered structure may include a step of irradiating the precursor layer of the layer (YA) or the layer (YA) with ultraviolet rays. The ultraviolet irradiation may be carried out at any stage after the step (II) (for example, after the removal of the solvent of the applied coating solution (U) is almost completed). The method is not specifically limited, A well-known method is applicable. The wavelength of the irradiated ultraviolet light is preferably in the range of 170 to 250 nm, more preferably in the range of 170 to 190 nm and/or in the range of 230 to 250 nm. Moreover, you may irradiate radiation, such as an electron beam and a gamma ray, instead of ultraviolet irradiation. By irradiating the ultraviolet rays, the gas barrier performance of the multilayered structure may be more highly expressed.

In order to arrange the adhesive layer (H) between the substrate (X) and the layer (YA), before applying the coating solution (U), the surface of the substrate (X) is treated with a known anchor coating agent, or the surface of the substrate (X) When applying a well-known adhesive agent, it is preferable to perform an aging process. Specifically, it is preferable to leave the substrate (X) coated with the coating liquid (U) under a relatively low temperature for a long time after application of the coating liquid (U) and before the heat treatment step of step (III). It is preferable that it is less than 110 degreeC, and, as for the temperature of an aging process, it is more preferable that it is 100 degrees C or less, It is more preferable that it is 90 degrees C or less. Moreover, it is preferable that it is 10 degreeC or more, and, as for the temperature of an aging process, it is more preferable that it is 20 degreeC or more, and it is still more preferable that it is 30 degreeC or more. The time of the aging treatment is preferably in the range of 0.5 to 10 days, more preferably in the range of 1 to 7 days, and still more preferably in the range of 1 to 5 days. By performing this aging process, the adhesive force between the base material (X) and the layer (YA) becomes stronger.

[Process (IV)]

In the step (IV), the layer (Z) is formed on the substrate (X) (or on the layer (Y)) by applying the coating solution (V) containing the polymer (E) having a plurality of phosphorus atoms. Usually, the coating liquid (V) is a solution in which the polymer (E) is dissolved in a solvent.

The coating liquid (V) may be prepared by dissolving the polymer (E) in a solvent, or the solution obtained when the polymer (E) is prepared may be used as it is. When the solubility of a polymer (E) is low, you may accelerate|stimulate melt|dissolution by heat processing or ultrasonic processing.

The solvent used for the coating liquid (V) may be appropriately selected according to the type of the polymer (E), but is preferably water, alcohols, or a mixed solvent thereof. As long as it does not interfere with the dissolution of the polymer (E), the solvent may include ethers such as tetrahydrofuran, dioxane, trioxane and dimethoxyethane; ketones such as acetone and methyl ethyl ketone; glycols such as ethylene glycol and propylene glycol; glycol derivatives such as methyl cellosolve, ethyl cellosolve, and n-butyl cellosolve; glycerin; acetonitrile; amides such as dimethylformamide; dimethyl sulfoxide; You may contain sulfolane etc.

The solid content concentration of the polymer (E) in the coating liquid (V) is preferably in the range of 0.01 to 60 mass%, more preferably in the range of 0.1 to 50 mass%, from the viewpoint of storage stability and applicability of the solution, It is more preferable to exist in the range of 0.2-40 mass %. The solid content concentration can be obtained by the same method as described for the coating liquid (U).

From the viewpoint of the storage stability of the coating liquid (V) and the gas barrier properties of the multilayer structure, the pH of the solution of the polymer (E) is preferably in the range of 0.1 to 6.0, more preferably in the range of 0.2 to 5.0, 0.5 to 4.0 is more preferred.

The pH of the coating liquid (V) can be adjusted by a known method, for example, by adding an acidic compound or a basic compound. Examples of the acidic compound include hydrochloric acid, nitric acid, sulfuric acid, acetic acid, butyric acid, and ammonium sulfate. Examples of the basic compound include sodium hydroxide, potassium hydroxide, ammonia, trimethylamine, pyridine, sodium carbonate, and sodium acetate.

In addition, when it is necessary to control the viscosity of the coating liquid (V), for example, a method such as adjusting the concentration of the solid content, adjusting the pH, or adding a viscosity adjusting agent can be adopted. Examples of the viscosity modifier include carboxymethyl cellulose, starch, bentonite, gum tragacanth, stearate, alginate, methanol, ethanol, n-propanol, and isopropanol.

Further, the coating liquid (V) may be subjected to degassing and/or degassing treatment as necessary. As the method of the degassing and/or degassing treatment, there are, for example, methods by vacuum evacuation, heating, centrifugation, ultrasonic waves, and the like, but a method including evacuation can be preferably used.

As the viscosity of the coating liquid (V) when applied in the step (IV), the viscosity measured with a Brookfield rotational viscometer (SB type viscometer; rotor No. 3, rotational speed 60 rpm) is 1000 mPa·s at the temperature at the time of application It is preferably less than or equal to 500 mPa·s, and more preferably less than or equal to 500 mPa·s. When the viscosity is 1000 mPa·s or less, the leveling property of the coating liquid (V) can be improved, and a multilayered structure having a more excellent appearance can be obtained. The viscosity of the coating liquid (V) when applied in the step (IV) can be adjusted by concentration, temperature, or the like.

A method of applying the solution of the coating liquid (V) on the substrate (X) or the layer (Y) is not particularly limited, and a known method may be employed. Preferred methods include, for example, a casting method, a dipping method, a roll coating method, a gravure coating method, a screen printing method, a reverse coating method, a spray coating method, a kiss coating method, a die coating method, a metalling bar coating method, and a chamber doctor combination. A coat method, a curtain coat method, a bar coat method, etc. are mentioned.

Usually, in the step (IV), the layer (Z) is formed by removing the solvent in the coating solution (V). There is no restriction|limiting in particular in the method of removing a solvent, A well-known drying method can be applied. Specifically, drying methods, such as a hot air drying method, a hot roll contact method, an infrared heating method, and a microwave heating method, can be applied individually or in combination. It is preferable that a drying temperature is 0-15 degreeC or more lower than the flow initiation temperature of the base material (X). The drying temperature is preferably in the range of 70 to 200°C, more preferably in the range of 80 to 180°C, still more preferably in the range of 90 to 160°C. You may perform removal of a solvent either under normal pressure or under reduced pressure. In the case where the step (IV) is performed following the step (II), the solvent may be removed by the heat treatment in the step (III) described above.

When the layer (Z) is laminated on both surfaces of the layered substrate (X) with or without the layer (Y), the coating solution (V) is applied to one side and then the solvent is removed to remove the first layer (Z) ), then, after applying the coating solution (V) to the other surface, the second layer (Z) may be formed by removing the solvent. The composition of the coating liquid (V) applied to each surface may be the same or different.

When the layer (Z) is laminated on a plurality of surfaces of the base material (X) having a three-dimensional shape with or without the layer (Y) interposed therebetween, the layer (Z) may be formed on each surface by the above method. . Alternatively, the plurality of layers (Z) may be formed simultaneously by applying the coating liquid (V) to a plurality of surfaces at the same time and drying the coating liquid (V).

As described above, the process is typically carried out in the order of (I), (II), (III), and (IV), but the layer (Z) is formed between the substrate (X) and the layer (Y). In this case, what is necessary is just to implement the process (IV) before the process (II), and it is also possible to implement the process (III) after the process (IV). From the viewpoint of obtaining a multilayered structure excellent in appearance, it is preferable to carry out the step (IV) after the step (III).

The multilayer structure thus obtained can be used as it is as the multilayer structure of the present invention. However, the multilayer structure of the present invention may be obtained by further bonding or forming other members (such as other layers) to the multilayer structure as described above. Adhesion of the said member can be performed by a well-known method.

In one aspect, the production method of the present invention comprises a step (W) of forming a layer (Y) containing aluminum atoms, and a coating solution (V) containing a polymer (E) having a plurality of phosphorus atoms. and the step (IV) of forming the layer (Z). As described above, when the layer (Y) is the layer (YA), the step (W) may include steps (I), (II) and (III). In addition, when the layer (Y) is the layer (YB) or the layer (YC), the step (W) may include a step of forming these layers by a vapor deposition method.

Example

Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited in any way by a following Example. In addition, each measurement and evaluation in an Example and a comparative example were implemented by the method of the following (1)-(4).

(1) Infrared absorption spectrum of layer (Y)

The infrared absorption spectrum of the layer (YA) formed in the Example was measured with the following method.

First, regarding the layer (YA) laminated on the substrate (X), the infrared absorption spectrum was measured using a Fourier transform infrared spectrophotometer (manufactured by Perkin Elmer, "Spectrum One"). The infrared absorption spectrum was measured in the range of ^{700 to 4000 cm -1} in the mode of ATR (total reflection measurement). When the thickness of the layer (YA) is 1 µm or less, an absorption peak derived from the substrate (X) is detected in the infrared absorption spectrum by the ATR method, and the absorption intensity derived only from the layer (YA) cannot be accurately obtained in some cases. . In this case, only the peak derived from the layer (X) was extracted by separately measuring the infrared absorption spectrum of only the base material (X) and subtracting it. In addition, even when the layer YA is laminated|stacked on the layer Z, the same method is employable. In addition, when the layer (YA) is formed inside the multilayer structure (for example, in the case of having a stacking order of the base material (X)/layer (YA)/layer (Z)), infrared absorption of the layer (YA) The spectrum can be obtained by measuring the infrared absorption spectrum of the exposed layer (YA) by measuring it before forming the layer (Z), or by peeling it off at the interface of the layer (YA) after forming the layer (Z) .

Based on the infrared absorption spectrum of the layer (YA) thus obtained, the maximum absorption wave number (n ^{1 ) in the range of 800 to 1400 cm -1} , and the absorbance (α ¹ ) at the maximum absorption wave number (n ^{1 )} ) was found. ^{In addition, the maximum absorption wave number (n 2} ) based on the stretching vibration of the hydroxyl group in the range of 2500 to 4000 cm ^-1 , and the absorbance (α ² ) at the maximum absorption wave number (n ^{2 ) were determined.} In addition, the half-width of the absorption peak of the maximum absorption wavenumber (n ¹ ) is obtained by obtaining two wavenumbers having an absorbance (absorbance (α ^{1 )/2) of half of the absorbance (α 1 ) in the absorption peak, and these} It was obtained by calculating the difference in wavenumbers. In addition, when the absorption peak of the maximum absorption wavenumber (n ¹ ) overlaps with the absorption peak derived from another component, it is separated into absorption peaks derived from each component by the least squares method using a Gaussian function. Then, as in the above case, the half width of the absorption peak of the ^{maximum absorption wave number (n 1 ) was obtained.}

(2) Appearance of multilayer structure

The appearance of the obtained multilayered structure was visually evaluated as follows.

A: It was colorless, transparent, uniform, and had a very favorable appearance.

B: A slight cloudiness or unevenness appeared, but it was a good appearance.

(3) Oxygen permeability (Os) under the conditions of 20°C and 85%RH

The oxygen permeability was measured using an oxygen permeation amount measuring device (“MOCON OX-TRAN2/20” manufactured by Modern Control). Specifically, the multilayer structure is set so that the layer (YZ) (or layer (YZ)) is directed to the oxygen supply side and the substrate (X) is directed to the carrier gas side, the temperature is 20°C, and the humidity on the oxygen supply side is 85% Oxygen permeability (unit: ml/(m 2 ·day·atm)) was measured under the conditions of RH, humidity on the carrier gas side of 85%RH, oxygen pressure of 1 atm, and carrier gas pressure of 1 atm. As the carrier gas, nitrogen gas containing 2% by volume of hydrogen gas was used.

(4) Oxygen permeability (Of) under conditions of 20°C and 85%RH after holding for 5 minutes in a state of 5% elongation under conditions of 23°C and 50%RH

A multilayer structure having a size of 21 cm × 30 cm was fabricated. Then, the multilayer structure was left under the conditions of 23° C. and 50% RH for 24 hours or more, and then stretched 5% in the longitudinal direction under the same conditions, and the stretched state was maintained for 5 minutes to obtain a multilayer structure after stretching. The oxygen permeability was measured using an oxygen permeation amount measuring device (“MOCON OX-TRAN2/20” manufactured by Modern Control). Specifically, the multilayer structure is set so that the layer YZ faces the oxygen supply side and the substrate X faces the carrier gas side, the temperature is 20° C., the humidity on the oxygen supply side is 85% RH, and the humidity on the carrier gas side The oxygen permeability (unit: ml/(m2·day·atm)) was measured under the conditions of 85%RH, oxygen pressure of 1 atm, and carrier gas pressure of 1 atm. As the carrier gas, nitrogen gas containing 2% by volume of hydrogen gas was used.

[Example of Preparation of Coating Solution (U)]

The manufacturing example of the coating liquid (U) used for manufacturing the layer (YA) is shown.

It heated up at 70 degreeC, stirring 230 mass parts of distilled water. 88 mass parts of aluminum isopropoxide was dripped at the distilled water over 1 hour, liquid temperature was gradually raised to 95 degreeC, and hydrolysis-condensation was performed by distilling the generated isopropanol. After adding 4.0 mass parts of 60 mass % nitric acid aqueous solution to the obtained liquid, and peptizing the aggregate of the particle|grains of a hydrolysis-condensation product by stirring at 95 degreeC for 3 hours, it concentrated so that the solid content concentration might become 10 mass % in terms of alumina. To 18.66 parts by mass of the dispersion thus obtained, 58.19 parts by mass of distilled water, 19.00 parts by mass of methanol, and 0.50 parts by mass of a 5 mass % polyvinyl alcohol aqueous solution were added and stirred to obtain a dispersion (S1). Moreover, 3.66 mass parts of 85 mass % phosphoric acid aqueous solution was used as a solution (T1). Subsequently, both the dispersion (S1) and the solution (T1) were adjusted to 15°C. Next, while maintaining the liquid temperature of 15° C., while stirring the dispersion (S1), the solution (T1) was added dropwise to obtain a coating solution (U1). While maintaining the obtained coating solution (U1) at 15°C, stirring was continued until the viscosity reached 1500 mPa·s. Further, the mole number of the metal atoms in the art coating liquid (U1), constituting the metal oxide (A) (alumina) (N _M) and the compound (B) number of moles of the atoms constituting the (phosphate) (N _P) ratio (molar number (N _M) / molar number (N _P)) of, was 1.15.

A coating solution (U2), a coating solution (U3), and a coating solution (U4) were respectively obtained in the same manner except that the ratio of _{N M} /N _{P was changed to 4.48, 1.92, and 0.82, respectively.}

[Example of Preparation of Coating Solution (V)]

A round-bottom flask equipped with a stirrer and a thermometer (volume: 50 ml) was replaced with nitrogen, and 2.5 g of water was poured as a solvent, and while stirring, 10 g of vinylphosphonic acid (hereinafter sometimes abbreviated as “VPA”), 2.5 g of water g and a mixed solution of 25 mg of 2,2'-azobis(2-amidinopropane) dihydrochloride (hereinafter sometimes abbreviated as "AIBA") was added dropwise to the round bottom flask. From this point on, a trace amount of nitrogen gas was continuously flowed through the entire polymerization process. The round-bottom flask was immersed in an oil bath and reacted at 80° C. for 3 hours, then the reaction mixture was diluted with 15 g of water and filtered through a cellulose membrane (“Spectra/Por” (trade name) manufactured by Spectrum Laboratories). Next, the solution of the filtrate was distilled off by an evaporator and vacuum dried at 50 DEG C for 24 hours to obtain a white polymer. As a result of measuring the molecular weight of this polymer by gel permeation chromatography and using a 1.2 wt% aqueous NaCl solution as a solvent at a polymer concentration of 0.1 wt%, the number average molecular weight was about 10,000 in terms of polyethylene glycol.

The purified polymer was dissolved in a mixed solvent of water and methanol at a concentration of 10 wt% to obtain a coating solution (V1).

A coating solution (V2) composed of a homopolymer of 4-vinylbenzyl phosphonic acid (hereinafter, sometimes abbreviated as “VBPA”) was obtained in the same manner as for preparing the coating solution (V1). Similarly, the coating solution (V3) and the coating solution (V4) of a copolymer obtained by copolymerizing VPA and methacrylic acid (hereinafter, sometimes abbreviated as “MA”) in molar ratios of 2/1 and 1/1, respectively each was obtained.

[Example 1]

As a base material, a stretched polyethylene terephthalate film (manufactured by Toray Corporation, "Lumira P60" (trade name), 12 µm thick, hereinafter sometimes abbreviated as "PET") was prepared. On the base material (PET), the coating solution (U1) was applied with a bar coater to a thickness of 0.5 µm after drying, and dried at 110°C for 5 minutes. Then, heat treatment was performed at 180° C. for 1 minute to obtain a structure (A1) having a structure of layer (Y1) (0.5 µm)/PET (12 µm). Next, on the layer (Y1) of the structure (A1), the coating solution (V1) is applied with a bar coater so that the thickness after drying becomes 0.3 μm, and dried at 110° C. for 5 minutes, whereby the layer (Z1) (0.3 μm)/ The multilayer structure (B1) of the present invention having a structure called layer (Y1) (0.5 mu m)/PET (12 mu m) was obtained.

The water vapor transmission rate (water vapor transmission rate; WVTR) of the obtained multilayered structure (B1) was measured using a water vapor transmission amount measuring device (“MOCON PERMATRAN3/33” manufactured by Modern Control). Specifically, the multilayer structure is set so that the layer Z1 faces the water vapor supply side and the PET layer faces the carrier gas side, and the temperature is 40° C., the humidity is 90%RH on the water vapor supply side, and the humidity is 0%RH on the carrier gas side. The moisture permeability (unit: g/(m 2 ·day)) was measured under the conditions of The water vapor transmission rate of the multilayer structure (B1) was 0.2 g/(m 2 ·day).

[Examples 2 to 3]

A multilayer structure was obtained in the same manner as in Example 1 except that the thickness of the layer (Z) was changed according to Table 1.

[Examples 4 to 6]

A multilayer structure was obtained in the same manner as in Example 1 except that the coating solution (V) to be used was changed according to Table 1.

[Examples 7 to 9]

A multilayer structure was obtained in the same manner as in Example 1, except that the conditions of heat treatment were changed according to Table 1.

[Examples 10 to 12]

A multilayer structure was obtained in the same manner as in Example 1 except that the coating solution (U) used was changed according to Table 1.

[Example 13]

A multilayer structure was obtained in the same manner as in Example 1, except that the heat treatment step was performed after the formation of the layer (Z).

[Example 14]

A multilayer structure was obtained in the same manner as in Example 1 except that the layers (Y) and (Z) were laminated on both sides of the substrate. As a result of measuring the water vapor transmission rate of the obtained multilayered structure in the same manner as in Example 1, it was 0.1 g (m 2 ·day) or less.

[Example 15]

Multilayered in the same manner as in Example 1, except that the base material was a stretched nylon film (“Enblem ON BC” (trade name), 15 μm thick, sometimes abbreviated as “ONY” manufactured by Yunichika Co., Ltd.) A construct was obtained.

[Example 16]

A multilayer structure was obtained in the same manner as in Example 1 except that the layer (Y) was formed after the formation of the layer (Z).

[Example 17]

A multilayer structure was obtained in the same manner as in Example 1, except that the layer (Y) was an aluminum vapor-deposited layer having a thickness of 0.03 µm. The aluminum layer was formed by the vacuum vapor deposition method.

[Example 18]

A multilayer structure was obtained in the same manner as in Example 1 except that the layer (Y) was a vapor-deposited layer of aluminum oxide having a thickness of 0.03 µm. The aluminum oxide layer was formed by vacuum deposition.

[Comparative Examples 1 to 18]

In Examples 1 to 18, those in which the layer (Z) was not formed were referred to as Comparative Examples 1 to 18.

[Comparative Example 19]

A multilayer structure was obtained in the same manner as in Example 1, except that the layer (Y) was a layer (Y') which was a vapor-deposited layer of silicon oxide having a thickness of 0.03 µm. The silicon oxide layer was formed by vacuum deposition.

[Comparative Example 20]

A multilayer structure was obtained in the same manner as in Example 1 except that the layer (Y) was not formed.

[Comparative Example 21]

A multilayer structure was obtained in the same manner as in Example 1 except that the layer (Z) was formed on PET. That is, in Comparative Example 20, the multilayer structure of Comparative Example 20 having a structure of layer (Y1) (0.5 µm)/PET (12 µm)/layer (Z1) (0.3 µm) was produced.

[Comparative Example 22]

In Comparative Example 19, the layer (Z) was not formed as Comparative Example 22.

[Comparative Example 23]

In Comparative Example 20, only the material in which the layer (Z) was not formed, that is, only the base material (PET) was used as Comparative Example 23.

The manufacturing conditions and evaluation results of the above Examples and Comparative Examples are shown in Tables 1 to 3 below. In addition, in the table, "-" means "not used", "cannot be calculated", "not implemented", "cannot be measured", and the like.

As is apparent from the table, the multilayer structures of Examples were able to maintain gas barrier properties at a high level even when subjected to strong stretching stress. In addition, the multilayered structures of Examples exhibited good external appearance.

[Example 19]

In Example 19, a longitudinal umbilical cord filled seal bag was fabricated using the multilayer structure of the present invention. First, in the same manner as in Example 1, a multilayer structure B1 was produced. Next, a two-component adhesive (manufactured by Mitsui Taketake Chemical Co., Ltd., A-520 (trade name) and A-50 (trade name)) was coated on the multilayer structure (B1) to dry it, and this and a stretched nylon film were prepared. (ONY described above) was laminated to obtain a laminate. Then, on the stretched nylon film of the laminate, a two-component adhesive (manufactured by Mitsui Taketake Chemical Co., Ltd., A-520 (trade name) and A-50 (trade name)) was coated and dried to prepare, and this An unstretched polypropylene film (manufactured by Tocelo Corporation, RXC-21 (trade name), 70 µm thick, hereinafter sometimes abbreviated as "CPP70") was laminated. In this way, a multilayer structure (C19) having a structure of PET/layer (Y1)/layer (Z1)/adhesive/ONY/adhesive/CPP70 was obtained.

Next, the multilayer structure (C19) was cut to a width of 400 mm, and supplied to a vertical umbilical cord filling packaging machine (manufactured by Orihiro Corporation) to produce a vertical umbilical cord filling seal bag (160 mm wide, 470 mm long) of the closure bonding type. did. Next, using an umbilical cord filling packaging machine, 2 kg of water was filled into the vertical umbilical cord filling seal bag made of the multilayer structure (C19). The workability of the multilayer structure (C19) in the umbilical cord filling packaging machine was good, and defects such as wrinkles and streaks did not appear in the appearance of the obtained vertical umbilical cord filling seal bag.

[Example 20]

In Example 20, a vacuum packaging bag was fabricated using the multilayer structure of the present invention. First, in the same manner as in Example 1, a multilayer structure B1 was produced. Next, a two-component adhesive (manufactured by Mitsui Taketake Chemical Co., Ltd., A-520 (trade name) and A-50 (trade name)) was coated on a stretched nylon film (ONY above) and dried to prepare, and The multilayer structure (B1) was laminated. Next, on the laminated multilayer structure (B1), a two-component adhesive (manufactured by Mitsui Taketake Chemical Co., Ltd., A-520 (trade name) and A-50 (trade name)) was coated and dried to prepare, and An unstretched polypropylene film (CPP70 described above) was laminated. In this way, a multilayer structure (C20) having a structure of ONY/adhesive/layer (Z1)/layer (Y1)/PET/adhesive/CPP70 was obtained.

Next, from the multilayer structure C20, two stacks of 22 cm x 30 cm in the longitudinal direction were cut out. Then, two sheets of multilayer structures C20 were stacked so that CPP70 was inside, and the three sides of the rectangle were heat-sealed to form a bag. The bag was filled with wooden spheres (30 mm in diameter) as a model of a solid food in a state where the spheres were tightly spread on the first layer so that the spheres were in contact with each other. Thereafter, the air inside the bag was degassed and the last side was heat-sealed to produce a vacuum package. In the obtained vacuum package, the multilayer structure C20 was in a state in close contact with the unevenness of the spherical body.

[Example 21]

In Example 21, a pouch with spout was fabricated using the multilayer structure of the present invention. First, in the same manner as in Example 19, a multilayer structure (C21) having a structure of PET/layer (Y1)/layer (Z1)/adhesive/ONY/adhesive/CPP70 was obtained. Next, after cutting out two multilayer structures C21 into a predetermined shape, two sheets of multilayer structures C21 are overlapped so that CPP70 is inside, heat-sealing the periphery, and heat-sealing a polypropylene spout was installed by In this way, a flat pouch-type pouch with spout could be produced without any problem.

[Example 22]

In Example 22, a laminate tube container was fabricated using the multilayer structure of the present invention. First, in the same manner as in Example 1, a multilayer structure B1 was produced. Next, to each of the two unstretched polypropylene films (manufactured by Tocelo Corporation, RXC-21 (trade name), 100 μm thick, hereinafter sometimes abbreviated as “CPP100”), a two-component adhesive (Mitsui) Takeda Chemical Co., Ltd., A-520 (trade name) and A-50 (trade name)) were coated and dried, and laminated with the multilayer structure (B1). In this way, a multilayer structure (C22) having a structure of CPP100/adhesive/layer (Z1)/layer (Y1)/PET/adhesive/CPP100 was obtained.

Next, after cutting out the multilayer structure C22 into a predetermined shape, the cylindrical body was produced by heat-sealing the overlapping part as normal. Next, the cylindrical body was attached to the mandrel for tube container shaping|molding, and the conical trapezoid shoulder part and the front-end|tip part continuous with it were produced at one end of the cylindrical body. The shoulder part and the front-end|tip part were formed by compression-molding polypropylene resin. Next, a cap made of polypropylene resin was attached to the distal end. Next, the other end in which the cylindrical body is opened was heat-sealed. In this way, the laminate tube container could be produced without any problem.

[Example 23]

In Example 23, an infusion bag was manufactured using the multilayer structure of the present invention. First, in the same manner as in Example 19, a multilayer structure (C23) having a structure of PET/layer (Y1)/layer (Z1)/adhesive/ONY/adhesive/CPP70 was obtained. Next, after cutting out two multilayer structures C23 into a predetermined shape, two sheets of multilayer structures C23 are overlapped so that CPP70 is inside, heat-sealed around the periphery, and a propylene spout is applied to the heat seal installed by In this way, the infusion bag could be produced without any problem.

[Example 24]

In Example 24, a lid material for a container was produced using the multilayered structure of the present invention. First, in the same manner as in Example 19, a multilayer structure (C24) having a structure of PET/layer (Y1)/layer (Z1)/adhesive/ONY/adhesive/CPP70 was obtained. Next, the multilayer structure C24 was cut out in a circular shape with a diameter of 88 mm as a lid material for a container. Further, a columnar container having a diameter of 78 mm, a flange width of 6.5 mm, and a height of 30 mm, consisting of three layers of polyolefin layer/steel layer/polyolefin layer (Hiletflex HR78-84 manufactured by Toyo Sekan Co., Ltd.) was prepared. The container was almost completely filled with water, and the container lid member made of the multilayer structure C24 was heat-sealed to the flange portion. In this way, the container with a lid using the lid material for containers was able to be produced without a problem.

[Example 25]

In Example 25, a paper container was produced using the multilayer structure of the present invention. First, in the same manner as in Example 1, a multilayer structure B1 was produced. Next, an adhesive is applied to both sides of a 400 g/m2 paperboard, and then a polypropylene resin (hereinafter, sometimes abbreviated as "PP") is extruded and laminated on both sides of the paperboard to form a PP layer (thickness each) on both sides of the paperboard. 20 μm) was formed. After that, an adhesive is applied to the surface of one PP layer, the multilayer structure (B1) is laminated thereon, and an adhesive is applied to the surface of the multilayer structure (B1), and an unstretched polypropylene film (CPP70 described above) and pasted together. In this way, a multilayer structure (C25) having a configuration of PP/paperboard/PP/adhesive/layer (Z1)/layer (Y1)/PET/adhesive/CPP70 was produced. In the preparation of the multilayered structure (C25), an anchor coat agent was used if necessary. Using the multilayer structure (C25) thus obtained, a brick-shaped paper container could be produced without any problem.

[Example 26]

In Example 26, a vacuum insulator was produced using the multilayer structure of the present invention. First, in the same manner as in Example 20, a multilayer structure (C26) having a structure of ONY/adhesive/layer (Z1)/layer (Y1)/PET/adhesive/CPP70 was obtained. Next, after cutting out two multilayer structures C26 into a predetermined shape, two sheets of multilayer structures C26 were overlapped so that CPP70 was inside, and a bag was formed by heat-sealing three sides of a rectangle. Next, the heat insulating core material was filled from the opening of the bag, and the bag was sealed with a vacuum packaging machine (VAC-STAR 2500 type manufactured by Frimark GmbH) at a temperature of 20°C and an internal pressure of 10 Pa. In this way, the vacuum insulator was able to be produced without any problem. In addition, the silica fine powder dried in the atmosphere of 120 degreeC for 4 hours was used for the heat insulating core material.

[Example 27]

In Example 27, a solar cell module was manufactured using the multilayer structure of the present invention. First, in the same manner as in Example 1, a multilayer structure B1 was produced. Next, an amorphous silicon solar cell installed on a 10 cm square tempered glass is sandwiched between an ethylene-vinyl acetate copolymer having a thickness of 450 μm, and the layer (Z1) of the multilayer structure (B1) is bonded thereon to face each other. A solar cell module was fabricated. Bonding was performed by performing pressure-bonding for 9 minutes, after performing evacuation at 150 degreeC for 3 minutes. The solar cell module produced in this way operated well and showed favorable electrical output characteristics over a long period of time.

The multilayered structure of the present invention is excellent in gas barrier properties and has a good external appearance. Further, even when subjected to physical stress such as deformation or impact, the gas barrier property can be maintained at a high level. For this reason, the multilayered structure of the present invention can be suitably used as a packaging material for food, medicine, medical substrate, industrial substrate, clothing, and the like.

In addition, as uses other than packaging materials, display members such as a substrate film for LCD, a substrate film for organic EL, a substrate film for electronic paper, an encapsulation film for electronic devices, a film for PDP, a film for LEDs, a film for an IC tag, a solar film Electronic device related members, such as solar cell members, such as a battery module, the back sheet for solar cells, and the protective film for solar cells; The member for optical communication, the flexible film for electronic devices, the diaphragm for fuel cells, the sealing film for fuel cells, the board|substrate film of various functional films, etc. are mentioned as an example.

Claims (19)

A multilayer structure having one or more layers each of a substrate (X), a layer (Y), and a layer (Z),
said layer (Y) contains aluminum atoms, said layer (Z) contains a polymer (E) having a plurality of phosphorus atoms,
The polymer (E) is a polymer of at least one monomer containing vinylphosphonic acids,
At least one set of the layer (Y) and the layer (Z) are laminated adjacently,
wherein said layer (Y) is a layer (YA) containing a reaction product (R),
The reaction product (R) is a reaction product formed by reacting a metal oxide (A) containing aluminum and a phosphorus compound (B). The method according to claim 1, wherein at least one set of the substrate (X), the layer (Y) and the layer (Z) are in the order of the substrate (X)/the layer (Y)/the layer (Z) A multilayer structure having a laminated structure. The multilayer structure according to claim 2, wherein the polymer (E) is polyvinylphosphonic acid represented by the following formula (I).
Formula I

In the above formula (I),
n is a natural number. According to claim 1,
The multilayer structure, wherein in the infrared absorption spectrum of the layer (YA), ^{a wavenumber (n 1} ) at which infrared absorption in the range of ^{800 to 1400 cm −1} becomes the maximum is in the range of 1080 to 1130 cm ^{−1 .} The absorbance according to claim 4, wherein in the infrared absorption spectrum of the layer (YA), the ^{absorbance (α 1 ) at the wave number (n 1} ) and the absorbance (α ² ) at the wave number (n ² ) are the absorbance satisfies the relationship of (α ² )/absorbance (α ^{1 )≤0.2,}
The wave number n ² is a wave number at which infrared absorption based on stretching vibration of a hydroxyl group in the range of ^{2500 to 4000 cm -1} in the infrared absorption spectrum of the layer YA becomes maximum. The multilayer structure according to claim 4, wherein the half-width of the absorption peak of ^{the wavenumber (n 1 ) is 200 cm −1} or less. 5. The method according to claim 4, wherein the metal oxide (A) is a hydrolysis-condensation product of a compound (L) containing a metal atom (M) to which a hydrolyzable characteristic group is bonded;
The multilayer structure wherein the compound (L) contains at least one compound (L ^{1 ) represented by the following formula (II).}
Formula II

In the above formula (II),
X ¹ is selected from the group consisting of F, Cl, Br, I, R ² O-, R ³ C(=O)O-, (R ⁴ C(=O)) ₂ CH- and NO _{3 ,}
R ¹ , R ² , R ³ and R ⁴ are each selected from the group consisting of an alkyl group, an aralkyl group, an aryl group and an alkenyl group,
In the formula (II), when a plurality of X ¹ is present, these X ¹ may be the same as or different from each other,
In formula (II), when a plurality of R ¹ is present, these R ¹ may be the same as or different from each other,
In formula (II), when a plurality of R ² is present, these R ² may be the same as or different from each other,
In the formula (II), when a plurality of R ³ is present, these R ³ may be the same or different from each other,
In formula (II), when a plurality of R ⁴ is present, these R ⁴ may be the same or different from each other,
m represents the integer of 1-3. The multilayer structure according to claim 7, wherein the compound (L ¹ ) is at least one compound selected from aluminum triisopropoxide and aluminum tri s-butoxide. The multilayer structure according to claim 4, wherein the phosphorus compound (B) is at least one compound selected from the group consisting of phosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid, and derivatives thereof. _{The number of moles (N M} ) of the metal atoms (M) constituting the metal oxide (A) in the layer (YA) and the number of moles (N M ) of the phosphorus atoms derived from the phosphorus compound (B) in the layer (YA) ( N _P ) satisfies the relationship of 1.0≤(the number of moles (N _M ))/(the number of moles (N _{P ))≤3.6.} The multilayer structure according to claim 1, wherein the substrate (X) includes at least one layer selected from the group consisting of a thermoplastic resin film layer, a paper layer, and an inorganic vapor deposition layer. The multilayered structure according to claim 1, wherein the oxygen permeability under the conditions of 20°C and 85%RH is 2 ml/(m 2 ·day·atm) or less. The oxygen permeability according to claim 1, wherein the oxygen permeability under the conditions of 20°C and 85%RH after holding for 5 minutes in the state of being stretched 5% under the conditions of 23°C and 50%RH is 4 ml/(m2·day·atm) ) below, a multilayer structure. A method for manufacturing the multilayer structure according to claim 1, comprising:
and a step (IV) of forming the layer (Z) by applying a coating solution (V) containing the polymer (E). The method for producing a multilayer structure according to claim 14, wherein the polymer (E) is polyvinylphosphonic acid represented by the following formula (I).
Formula I

In the above formula (I),
n is a natural number. 15. The method of claim 14,
By mixing the metal oxide (A), at least one compound containing a site capable of reacting with the metal oxide (A), and a solvent, the metal oxide (A), the at least one compound and the solvent are Step (I) of preparing a coating liquid (U) containing;
Step (II) of forming a precursor layer of the layer (YA) on the substrate (X) by applying the coating solution (U) on the substrate (X);
Further comprising the step (III) of heat-treating the precursor layer of the layer (YA) at a temperature of 110 ° C. or higher to form the layer (YA),
the at least one compound contains the phosphorus compound (B),
In the above coating liquid (U), the molar number (N _M) and a mol number (N _P) of phosphorus atoms contained in the compound of (B) of the metal atom (M) constituting the metal oxide (A), 1.0 A method of manufacturing a multilayer structure, which satisfies the relationship of ≤(the number of moles (N _M ))/(the number of moles (N _{P ))≤3.6.} The method for manufacturing a multilayered structure according to claim 16, wherein the step (IV) is performed after the step (III).

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